CN107121891A - Colored curable resin composition, colour filter and liquid crystal display device - Google Patents

Colored curable resin composition, colour filter and liquid crystal display device Download PDF

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CN107121891A
CN107121891A CN201710101590.0A CN201710101590A CN107121891A CN 107121891 A CN107121891 A CN 107121891A CN 201710101590 A CN201710101590 A CN 201710101590A CN 107121891 A CN107121891 A CN 107121891A
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methyl
compound
ring
carbon number
acid
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CN107121891B (en
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朴昭妍
金兑昱
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Materials For Photolithography (AREA)
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  • Optical Filters (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

The present invention provides the colored curable resin composition of colour filter, the colour filter comprising it and the liquid crystal display device that can form that lightness is high, solvent resistance is good.Colored curable resin composition, it is containing colouring agent (A), resin glue (B), polymerizable compound (C), polymerization initiator (D) and epoxide (P) (but, it is different from resin glue (B)) colored curable resin composition, colouring agent (A) is the colouring agent of inclusion compound (Aa), the compound (Aa) is by the cation with pigment skeleton, with from containing from tungsten, molybdenum, at least one element and the anion of the compound of oxygen selected in silicon and phosphorus is constituted, relative to colouring agent (A) total amount, the containing ratio of epoxide (P) is more than 0.1 mass % and below 60 mass %.

Description

Colored curable resin composition, colour filter and liquid crystal display device
Technical field
The present invention relates to colored curable resin composition, colour filter and liquid crystal display device.
Background technology
Colored curable resin composition can be used for manufacture in liquid crystal display device, el display device and plasma The colour filter used in the display devices such as body display display device.It is used as such colored curable resin composition, it is known that There is the composition (patent document 1) for including colouring agent, resin, polymerizable compound and the polymerization initiator being expressed from the next.
[in formula (1), R1And R2Represent there can be the phenyl of substituent independently of each other.
R3And R4Represent that hydrogen atom contained in 1 valency saturated hydrocarbyl of carbon number 1~10, the saturated hydrocarbyl can independently of each other To be replaced by the aromatic hydrocarbyl or halogen atom of carbon number 6~10, contained hydrogen atom can be by carbon number 1 in the aromatic hydrocarbyl Contained-CH in the alkoxy substitution of~3 alkyl or carbon number 1~3, above-mentioned saturated hydrocarbyl2- can by-O- ,-CO- or- NR11- replace.
R1And R3The ring containing nitrogen-atoms, R can be formed together2And R4The ring containing nitrogen-atoms can be formed together.
R5Expression-OH ,-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8Or-SO2NR9R10。
R6And R7The alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.
M represents 0~4 integer.In the case of integers of the m for more than 2, multiple R5Can be with mutually the same, also can be different.
R8Represent that hydrogen atom contained in 1 valency saturated hydrocarbyl of carbon number 1~20, the saturated hydrocarbyl can be taken by halogen atom Generation.
Z+Represent+N(R11)4、Na+Or K+。
R9And R10The saturated hydrocarbyl of 1 valency of hydrogen atom or carbon number 1~20, R are represented independently of each other9And R10It can be combined with each other And form the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.
4 R11Hydrogen atom, the 1 valency saturated hydrocarbyl or the aralkyl of carbon number 7~10 of carbon number 1~20 are represented independently of each other.]
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-50693 publications
The content of the invention
The invention problem to be solved
But, in obtained colour filter, its lightness is low sometimes, and its solvent resistance is insufficient in addition.The problem of the present invention It is to provide and can forms the colored curable resin composition for the colour filter that lightness is high, solvent resistance is good.
Means for solving the problems
That is, main points of the present invention are as described below.
[1] colored curable resin composition, it is to contain colouring agent (A), resin glue (B), polymerizable compound (C), the colored curable resin group of polymerization initiator (D) and epoxide (P) (but, different from resin glue (B)) Compound,
Colouring agent (A) is the colouring agent of inclusion compound (Aa), compound (Aa) by the cation with pigment skeleton and From containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and the anion of the compound of oxygen composition,
Relative to colouring agent (A) total amount, the containing ratio of epoxide (P) is more than 0.1 mass % and 60 mass % Below.
[2] colored curable resin composition described in [1], wherein, resin glue (B) is with from from insatiable hunger With the construction unit (a) of at least one kind of monomer selected in carboxylic acid and unsaturated carboxylic acid anhydrides and from ethylenic unsaturated bond With the copolymer of the construction unit (b) of the monomer of ring-type ether structure.
[3] colored curable resin composition described in [1] or [2], wherein, by the cation with pigment skeleton and From the compound (Aa) containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and the anion of the compound of oxygen composition For the compound represented by formula (A-I).
[in formula (A-I), R41~R44The amino that can be substituted or the carbon that can be substituted with halogen atoms are represented independently of each other Contained methylene is replaced by oxygen atom in the saturated hydrocarbyl of number 1~20, the alkyl of carbon number 2~20, the alkyl of the carbon number 2~20 Group, can have substituent aromatic hydrocarbyl, can have substituent aralkyl or hydrogen atom.R41With R42It can combine simultaneously Ring, R are formed together with the nitrogen-atoms that they are combined43With R44It can combine and form ring together with the nitrogen-atoms that they are combined.
R47~R54The alkyl of hydrogen atom, halogen atom, nitro, hydroxyl or carbon number 1~8 is represented independently of each other, in structure Into pluggable oxygen atom between the methylene of the alkyl.R48With R52It can be combined with each other and form-NH- ,-O- ,-S- or-SO2-. R41~R44And R47~R54In, adjacent methylene will not be replaced by oxygen atom simultaneously, in addition, the methylene of the end of alkyl Also oxygen atom will not be replaced by.
Ring T1Represent there can be the heteroaromatic of substituent.
[Y]m-Represent containing at least one element and the anion of the m valencys of oxygen in tungsten, molybdenum, silicon and phosphorus.
M represents 2~14 integer.
Further, in the case of containing multiple cations represented by following formula in 1 molecule, they can be identical Structure, or different structures.
[in formula, ring T1、R41~R44And R47~R54Respectively with it is above-mentioned synonymous.]]
[4] colour filter formed as the colored curable resin composition described in any one of [1]~[3].
[5] liquid crystal display device, it includes the colour filter described in [4].
The effect of invention
In accordance with the invention it is possible to form the good colour filter of high brightness, solvent resistance.
Embodiment
The colored curable resin composition of the present invention contains colouring agent (A), resin glue (B), polymerizable compound (C), polymerization initiator (D) and epoxide (P) (but, different from resin glue (B)), total relative to colouring agent Amount, the epoxide (P) containing ormal weight.
＜ colouring agents (A) ＞
Colouring agent (A) is preferably to include by the cation with pigment skeleton and from containing from tungsten, molybdenum, silicon and phosphorus The compound (Aa) (hereinafter sometimes referred to compound (Aa)) that at least one element of selection and the anion of the compound of oxygen are constituted Colouring agent.Compound (Aa) can individually, also include two or more.In addition, as colouring agent (A), can further include dyestuff (Ab)。
Pigment skeleton in compound (Aa) refers to optionally absorb luminous ray (wavelength：400~750nm) and have The structure for being used for showing the feature with inherent colour is included in the part-structure of the compound of inherent colour, the part-structure.
The pigment skeleton having as the cation for constituting compound (Aa), can include azo skeleton, xanthene skeleton, a word used for translation Has structured pigment skeleton in piperazine skeleton, cyanines skeleton, acridine skeleton, the sour skeleton of anthraquinone skeleton and side etc.；Triarylmethane Skeleton；Making more than 1 of the aromatic series hydrocarbon ring of triarylmethane skeleton becomes pigment skeleton of heteroaromatic etc..Wherein, The xanthene skeleton for having imported structure, the cyanines skeleton for having imported structure can preferably be included, side's acid of structure has been imported Skeleton, triarylmethane skeleton and more than 1 of aromatic series hydrocarbon ring of triarylmethane skeleton is set to become heteroaromatic Pigment skeleton, can more preferably enumerating more than 1 of the aromatic series hydrocarbon ring for triarylmethane skeleton of sening as an envoy to, to become aromatic series miscellaneous The pigment skeleton of ring.
Basic compound as anion is to contain at least one element and the chemical combination of oxygen in tungsten, molybdenum, silicon and phosphorus Thing, for example, can include the combination of two or more (preferably 3 kinds) of polyacid in wolframic acid, molybdic acid, silicic acid and phosphoric acid； Contain at least one element and the isopolyacid of oxygen in tungsten, molybdenum, silicon and phosphorus；Contain 2 in tungsten, molybdenum, silicon and phosphorus Heteropoly acid of element above and oxygen etc..Wherein, as preferred compound, it can include in wolframic acid, molybdic acid and phosphoric acid Two or more (preferably 3 kinds) combination；Or the heteropoly acid containing tungsten and the isopolyacid containing tungsten, it is highly preferred that can enumerate Go out phosphotungstic acid, silico-tungstic acid and tungsten system isopolyacid.
As the heteropoly acid containing tungsten or the anion of isopolyacid, can for example include Keggin-type phosphotungstic acid ion α- [PW12O40]3-, Dawson type phosphotungstic acid ions α-[P2W218O62]6-、β-[P2W18O62]6-, Keggin-type silico-tungstic acid ion α- [SiW12O40]4-、β-[SiW12O40]4-、γ-[SiW12O40]4-、[P2W17O61]10-、[P2W15O56]12-、[H2P2W12O48]12-、 [NaP5W30O110]14-、α-[SiW9O34]10-、γ-[SiW10O36]8-、α-[SiW11O39]8-、β-[SiW11O39]8-、[W6O19]2-、 [W10O32]4-、WO4 2-With their mixture.
Anion be preferably also come the compound that freely at least one element in silicon and phosphorus and oxygen are constituted it is cloudy from Son.
The anion of the compound constituted as at least one element and oxygen that come freely in silicon and phosphorus, can be included SiO3 2-、PO4 3-。
From synthesis and post processing easy degree, preferably Keggin-type phosphotungstic acid ion, Dawson types phosphotungstic acid from The phosphotungstic anions such as son；Silico-tungstic acid the anion, [W such as Keggin-type silico-tungstic acid ion10O32]4-Deng tungsten system isopolyacid anion, Wherein, more preferably phosphotungstic anion, tungsten system isopolyacid anion.
As by the cation with xanthene pigment skeleton and from containing at least 1 selected from tungsten, molybdenum, silicon and phosphorus The compound (Aa) that the anion of the compound of individual element and oxygen is constituted, can include C.I. pigment red 81s, 81：1、81：2、81： 3、81：4、81：5、169；C.I. pigment violet 1,1：1、1：2、2、2：2 etc..
In addition, as by the cation with triarylmethane pigment skeleton and from containing from tungsten, molybdenum, silicon and phosphorus The compound (Aa) that at least one element of selection and the anion of the compound of oxygen are constituted, can include C.I. pigment blue 1s, 1： 2、1：3、2、2：1、2：2、3、8、9、10、10：1、11、12、18、19、24、24：1、53、56、56：1、57、58、59、61、62 Deng.
As compound (Aa), the compound (hereinafter also referred to (A-I)) preferably represented by formula (A-I).
[in formula (A-I), R41~R44The amino that can be substituted is represented independently of each other or can be substituted with halogen atoms Contained methylene is replaced by oxygen atom in the saturated hydrocarbyl of carbon number 1~20, the alkyl of carbon number 2~20, the alkyl of the carbon number 2~20 The group that changes, the aromatic hydrocarbyl can with substituent, the aralkyl or hydrogen atom can with substituent.R41With R42It can combine And form ring, R together with the nitrogen-atoms that they are combined43With R44It can combine and form ring together with the nitrogen-atoms that they are combined.
R47~R54Hydrogen atom, halogen atom, nitro, hydroxyl, the alkyl of carbon number 1~8 are represented independently of each other, are being constituted Oxygen atom is can be inserted between the methylene of the alkyl.R48With R52It can be combined with each other and form-NH- ,-O- ,-S- or-SO2-。
R41~R44And R47~R54In, adjacent methylene will not be replaced by oxygen atom simultaneously, in addition, the end of alkyl Methylene will not also be replaced by oxygen atom.
Ring T1Represent there can be the heteroaromatic of substituent.
[Y]m-Represent containing at least one element and the anion of the m valencys of oxygen in tungsten, molybdenum, silicon and phosphorus.
M represents 2~14 integer.
Further, in the case of containing multiple cations represented by following formula in 1 molecule, they can be identical Structure, or different structures.
[in formula, ring T1、R41~R44And R47~R54Respectively with it is above-mentioned synonymous.]]
Ring T1Heteroaromatic can be monocyclic, or fused rings.In addition, heteroaromatic is preferably 5~10 Yuan of rings, more preferably 5~9 yuan of rings.As monocyclic heteroaromatic, can for example include pyrrole ring, oxazole rings, pyrazole ring, 5 yuan of rings containing nitrogen-atoms such as imidazole ring, thiazole ring；5 yuan of rings of the not nitrogen atom such as furan nucleus, thiphene ring；Pyridine ring, pyrimidine 6 yuan of rings containing nitrogen-atoms such as ring, pyridazine ring, pyrazine ring etc., as the heteroaromatic of fused rings, can include indole ring, The fused rings containing nitrogen-atoms such as benzimidazole ring, benzothiazole ring, quinoline ring；The fusion of the not nitrogen atom such as benzofuran ring Ring etc..
It is used as ring T1The substituent that can have of heteroaromatic, halogen atom, cyano group can be included, can have halogen former The alkyl of the carbon number 1~20 of the substituents such as son, can have the carbon numbers 6 of the substituents such as the alkyl of halogen atom or carbon number 1~10~ 20 aromatic hydrocarbyl, there can be amino of substituent such as alkyl of carbon number 1~10 etc..
Wherein, ring T1Heteroaromatic be preferably the heteroaromatic containing nitrogen-atoms, more preferably contain nitrogen-atoms 5 yuan of rings heteroaromatic.
In addition, ring T1The ring more preferably represented by formula (Ab2-x1).
[ring T2Represent heteroaromatic.
R45And R46Represent can there is saturated hydrocarbyl, the alkane of carbon number 2~20 of the carbon number 1~20 of substituent independently of each other Contained methylene is replaced by oxygen atom in base, the alkyl of the carbon number 2~20 group, the aromatic hydrocarbon can with substituent Base, the aralkyl or hydrogen atom can with substituent.R45With R46It can combine and form ring together with the nitrogen-atoms that they are combined.
But, adjacent methylene will not be replaced by oxygen atom simultaneously, in addition, the methylene of the end of alkyl also will not It is replaced by oxygen atom.R55Represent the saturated hydrocarbyl of carbon number 1~20 or there can be the aromatic hydrocarbyl of substituent.
K1 represents 0 or 1.
* the bonding end with carbocation is represented.]
It is used as ring T2Heteroaromatic, can include and ring T1The same ring of the heteroaromatic of middle illustration.
And then, ring T1The ring more preferably represented by formula (Ab2-y1).
[R56Represent hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or there can be the aromatic hydrocarbon of the carbon number 6~20 of substituent Base.
X2 represents oxygen atom ,-NR57- or sulphur atom.
R57Represent the alkyl of hydrogen atom or carbon number 1~10.
R45And R46With it is above-mentioned synonymous.
* the bonding end with carbocation is represented.]
In addition, ring T1The ring preferably also represented by formula (Ab2-x2).
[ring T3Represent the heteroaromatic of 5~10 yuan of rings with nitrogen-atoms.
R58The aromatic hydrocarbyl of the saturated hydrocarbyl for representing carbon number 1~20 or the carbon number 6~20 can with substituent.
R59Represent hydrogen atom, can have substituent carbon number 1~20 saturated hydrocarbyl, can have substituent carbon number 6~ 20 aromatic hydrocarbyl or the aralkyl can with substituent.
K2 represents 0 or 1.
* the bonding end with carbocation is represented.]
In addition, ring T1The ring further preferably also represented by formula (Ab2-y2).
[R60Represent hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or there can be the aromatic hydrocarbon of the carbon number 6~20 of substituent Base.
R59Represent with it is above-mentioned synonymous.
* the bonding end with carbocation is represented.]
By R41~R46、R55、R56And R58~R60The saturated hydrocarbyl of the carbon number 1~20 of expression can for straight chain, branched chain and Ring-type it is any.As straight chain or the saturated hydrocarbyl of branched chain, can include methyl, ethyl, propyl group, butyl, amyl group, oneself The straight-chain alkyls such as base, octyl group, nonyl, decyl, dodecyl, cetyl and eicosyl；Isopropyl, isobutyl group, isoamyl Point branched-chain alkyl such as base, neopentyl and 2- ethylhexyls etc..The carbon number of the saturated hydrocarbyl is preferably 1~10, more preferably 1~ 8, more preferably 1~6.
By R41~R46、R55、R56And R58~R60The saturated hydrocarbyl of the ring-type of expression can be monocyclic or polycyclic.Make For the saturated hydrocarbyl of the ring-type, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl and adamantyl etc. can be included.The ring-type it is full Carbon number with alkyl is preferably 3~10, and more preferably 6~10.
R41~R46、R55、R56And R58~R60Saturated hydrocarbyl can be by halogen atom or substituted or unsubstituted amino Substitution.As substituted or unsubstituted amino, for example, it can include amino；The alkyl ammonia such as dimethylamino and diethylamino Base.As halogen atom, fluorine, chlorine, bromine and iodine etc. can be included.In the case that halogen atom is fluorine atom, preferably as formed three The such halogen atom substitution of the perfluoroalkyl units such as methyl fluoride unit, pentafluoroethyl group unit and heptafluoropropyl unit.
As the saturated hydrocarbyl of such carbon number 1~20 that instead of with substituted-amino or halogen atom, for example, it can enumerate Go out the group represented by following formula.In following formula, * represents the bonding end with nitrogen-atoms.
As by R47~R54The alkyl of the carbon number 1~8 of expression, can be included as by R41The saturated hydrocarbyl of expression is illustrated Straight chain or branched chain saturated hydrocarbyl in carbon number 1~8 group.
In addition, as by R57The alkyl of the carbon number 1~10 of expression, can be included as by R41The saturated hydrocarbyl example of expression The group of carbon number 1~10 in the straight chain or the saturated hydrocarbyl of branched chain that show.
Just by R41~R54For the alkyl of expression, contained methylene can be replaced by oxygen atom in the alkyl.Alkyl It is preferred that carbon number be 2~10, more preferably 2~8.When being additionally inserted into oxygen atom, between end and oxygen atom or oxygen atom with Carbon number between oxygen atom is, for example, 1~5, preferably 2~3, more preferably 2.But, adjacent methylene will not simultaneously by for Oxygen atom is changed to, in addition, the methylene of the end of alkyl will not also be replaced by oxygen atom.In preferred concrete example, it can arrange Enumerate the group represented by following formula.In following formula, * represents the bonding end with nitrogen-atoms.
In the group that contained methylene substituted for by oxygen atom in such alkyl, such as comprising alkoxyalkyl； Or (alkyloxy-alkoxy) alkyl, (alkoxyalkyoxyalkoxy) alkyl, (alkoxyalkyoxyalkoxy alkoxy) alkane Base, (alkoxyalkyoxyalkoxy alkyloxy-alkoxy) alkyl, (alkoxyalkyoxyalkoxy alkyloxy-alkoxy alcoxyl Base) the poly-alkoxyl alkyl such as alkyl etc., the repeat number of oxyalkyl units is, for example, 1~6, preferably 1~4, more preferably 1~2.
In addition, by R41~R46、R55、R56And R58~R60The aromatic hydrocarbon of the carbon number 6~20 with substituent represented The carbon number of base is preferably 6~15, more preferably carbon number 6~12.As the aromatic hydrocarbyl, phenyl, tolyl, two can be included Tolyl, naphthyl, anthryl, phenanthryl, xenyl, terphenyl etc., can preferably include phenyl, naphthyl, tolyl and diformazan Phenyl, it is highly preferred that phenyl can be included.In addition, the aromatic hydrocarbyl there can be the substituent of more than 1 or 2, taken as this Dai Ji, can include the halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atoms；The carbon number such as chloromethyl and trifluoromethyl 1~ 6 haloalkyl；The alkoxy of the carbon number such as methoxyl group and ethyoxyl 1~6；Hydroxyl；Sulfamoyl；The carbon numbers such as methyl sulphonyl 1 ~6 alkyl sulphonyl；Alkoxy carbonyl of the carbon number such as methoxycarbonyl and ethoxy carbonyl 1~6 etc..It is used as what can be substituted The concrete example of aromatic hydrocarbyl, for example, can include the group represented by following formula.In following formula, * represents the key with nitrogen-atoms Close end.
As by R41~R46、R59The aralkyl with substituent represented, can include methylene, ethylidene, Asia third Group that the alkylidene of the carbon numbers such as base 1~5 is combined into the group illustrated as above-mentioned aromatic hydrocarbyl etc..
It is used as R41And R42With reference to and with the ring, the R that are formed together with their nitrogen-atoms for combining43And R44Tied with reference to and with them Ring and R that the nitrogen-atoms of conjunction is formed together45And R46With reference to and with the ring that is formed together with their nitrogen-atoms for combining, it can enumerate Go out the nitrogenous yuan of rings of non-aromatic 4~7 such as pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, can preferably include pyrrolidine ring, Piperidine ring etc. only there is 1 nitrogen-atoms to be used as heteroatomic 4~7 yuan of rings.
Wherein, as R41~R44、R55、R56、R58And R59, preferably the saturated hydrocarbyl of carbon number 1~20 or can have substituent Aromatic hydrocarbyl, the more preferably independently of one another saturated hydrocarbyl of carbon number 1~8 or the aromatic hydrocarbyl represented by following formula. R55Aromatic hydrocarbyl further preferably to be represented by following formula.In following formula, * represents the bonding end with nitrogen-atoms.
R45~R46It is preferred that be independently of one another carbon number 1~20 saturated hydrocarbyl, carbon number 2~20 alkyl carbon atom Between insert the group of oxygen atom or can have the aromatic hydrocarbyl of substituent, or R45With R46With reference to and with they combine Nitrogen-atoms forms ring together.Preferred scheme is following proposal：R45~R46The independently of one another saturated hydrocarbons of carbon number 1~8 Base, alkoxyalkyl or the aromatic hydrocarbyl represented by following formula, or R45With R46With reference to and being formed only has 1 nitrogen-atoms It is used as heteroatomic 4~7 yuan of rings.In following formula, * represents the bonding end with nitrogen-atoms.
In addition, as by R47~R54The carbon atom of the alkyl of the carbon number 1~8 of expression and the alkyl in carbon number 2~8 interleaves Entered the group of oxygen atom, can include from above-mentioned R41~R46The base of group of the carbon number below 8 is have selected in corresponding group Group, it is highly preferred that the group represented by following formula can be included.In following formula, * represents the bonding end with carbon atom.
From the easy degree aspect of synthesis, R47~R54It is preferred that being independently of one another hydrogen atom, halogen atom or carbon number 1~8 alkyl, more preferably independently of one another hydrogen atom, methyl, fluorine atom or chlorine atom.
As formula (Ab2) cationic moiety, it can include as shown in table 1 below by formula (Ab2-1) expression 1~cation of cation 14 etc..In table, * represents bonding end.
【Table 1】
In table 1, Ph1~Ph9 represents the group represented by following formula.In formula, * represents bonding end.
In addition, as formula (Ab2) cationic moiety, can also include as shown in table 2 below by formula (Ab2-2) 15~cation of cation 18 of expression etc..In table, * represents bonding end.
【Table 2】
R41 R42 R43 R44 R59 R60
Cation 15 CH2CH3 CH2CH3 CH2CH3 CH2CH3 CH3 Ph1
Cation 16 Cll2Cll3 Cll2Cll3 Cll2Cll3 Cll2Cll3 (Cll2)5Cll3 Ph10
Cation 17 CH2CH(CH3)CH3 CH2CH(CH3)CH3 CH2CH(CH3)CH3 CH2CH(CH3)CH3 CH3 Ph1
Cation 18 CH2CH3 Ph1 CH2CH3 Ph1 (CH2)5CH3 Ph11
In table 2, Ph1, Ph10, Ph11 represent the group represented by following formula.In formula, * represents bonding end.
Wherein, as formula (Ab2) cationic moiety, 1~cation of preferred cationic 6,11~cation of cation 14, More preferably cation 1, cation 2 or 12~cation of cation 14, further preferred cation 12.
As compound (Aa), the compound represented by following formula can be included.
【Table 3】
Compound (Aa) Cation m Anion
(Aa2-1) Cation 1 3 [PW12O40]3-
(Aa2-2) Cation 1 6 [P2W18O62]6-
(Aa2-3) Cation 1 4 [SiW12O40]4-
(Aa2-4) Cation 1 4 [W10O32]4-
(Aa2-5) Cation 2 3 [PW12O40]3-
(Aa2-6) Cation 2 6 [P2W18O62]6-
(Aa2-7) Cation 2 4 [SiW12O40]4-
(Aa2-8) Cation 2 4 [W10O32]4-
(Aa2-9) Cation 4 3 [PW12O40]3-
(Aa2-10) Cation 4 6 [P2W18O62]6-
(Aa2-11) Cation 4 4 [SiW12O40]4-
(Aa2-12) Cation 4 4 [W10O32]4-
(Aa2-13) Cation 5 3 [PW12O40]3-
(Aa2-14) Cation 5 6 [P2W18O62]6-
(Aa2-15) Cation 5 4 [SiW12O40]4-
(Aa2-16) Cation 5 4 [W10O32]4-
(Aa2-17) Cation 6 3 [PW12O40]3-
(Aa2-18) Cation 6 6 [P2W18O62]6-
(Aa2-19) Cation 6 4 [SiW12O40]4-
(Aa2-20) Cation 6 4 [W10O32]4-
(Aa2-21) Cation 7 3 [PW12O40]3-
(Aa2-22) Cation 7 6 [P2W18O62]6-
(Aa2-23) Cation 7 4 [SiW12O40]4-
(Aa2-24) Cation 7 4 [W10O32]4-
(Aa2-25) Cation 8 3 [PW12O40]3-
(Aa2-26) Cation 8 6 [P2W18O62]6-
(Aa2-27) Cation 8 4 [SiW12O40]4-
(Aa2-28) Cation 8 4 [W10O32]4-
【Table 4】
Compound (Aa) Cation m Anion
(Aa2-29) Cation 9 3 [PW12O40]3-
(Aa2-30) Cation 9 6 [P2W18O62]6-
(Aa2-31) Cation 9 4 [SiW12O40]4-
(Aa2-32) Cation 9 4 [W10O32]4-
(Aa2-33) Cation 10 3 [PW12O40]3-
(Aa2-34) Cation 10 6 [P2W1aO62]6-
(Aa2-35) Cation 10 4 [SiW12O40]4-
(Aa2-36) Cation 10 4 [W10O32]4-
(Aa2-37) Cation 11 3 [PW12O40]3-
(Aa2-38) Cation 11 6 [P2W18O62]6-
(Aa2-39) Cation 11 4 [SiW12O40]4-
(Aa2-40) Cation 11 4 [W10O32]4-
(Aa2-41) Cation 13 3 [PW12O40]3-
(Aa2-42) Cation 13 6 [P2W18O62]6-
(Aa2-43) Cation 13 4 [SiW12O40]4-
(Aa2-44) Cation 13 4 [W10O32]4-
(Aa2-45) Cation 14 3 [PW12O40]3-
(Aa2-46) Cation 14 6 [P2W18O62]6-
(Aa2-47) Cation 14 4 [SiW12O40]4-
(Aa2-48) Cation 14 4 [W10O32]4-
(Aa2-49) Cation 15 3 [PW12O40]3-
(Aa2-50) Cation 15 6 [P2W18O62]6-
(Aa2-51) Cation 15 4 [SiW12O40]4-
(Aa2-52) Cation 15 4 [W10O32]4-
(Aa2-53) Cation 17 3 [PW12O40]3-
(Aa2-54) Cation 17 6 [P2W18O62]6-
(Aa2-55) Cation 17 4 [SiW12O40]4-
(Aa2-56) Cation 17 4 [W10O32]4-
Wherein, compound is preferably the compound represented by formula (Aa2-53).
Can be according to the method system described in Japanese Unexamined Patent Publication 2015-28121 publications as the compound that formula (A-I) is represented Make.
Dyestuff (Ab)
As dyestuff, for example, it can include in colour index that (The Society of Dyers and Colourists go out Version) in be categorized in the compound of the material with tone beyond pigment, dyeing and take down notes known dye described in (Se Ran societies) Material.
As dyestuff, for example, it can include azo dyes (such as monoazo dyes, diazo colours, azidine dye, metal network Salt azo dyes etc.), anthraquinone dye, indigo based dye, phthalocyanine dye, pyrazolone dye, stibene dyestuff, class Hu trailing plants Bu Su dyestuffs, thiazole dye, quinoline dye, triarylmethane colouring matters, triarylmethane dye, acridine dye, xanthene dye, a word used for translation Piperazine dyestuff, thiazine dye, oxazine dyes, cyanine dyes, indamines dyestuff, indophenol dye, naphthalimide dye, perylenes dyestuff, Naphthoquinone dyestuff, quinoneimine dye, methine dyes, methylene amine dyestuff, squaraine dye, styryl dye, coumarine dye, quinoline Quinoline dyestuff, tetraazatetradecane porphyrin dyestuff, nitro dye or nitroso-dyes etc., these are preferably organic solvent-soluble.These dyes Material can be used alone or two or more is applied in combination.
Wherein, preferably xanthene dye, triarylmethane dye, coumarine dye, anthraquinone dye, tetraazatetradecane porphyrin dyestuff, It is azo dyes, thiazine dye, oxazine dyes, phthalocyanine dye, quinophthalone dyestuff, cyanine dyes, naphthoquinone dyestuff, quinoneimine dye, secondary Methyl dyestuff, methylene amine dyestuff, squaraine dye, acridine dye, styryl dye, quinoline dye and nitro dye, more preferably Xanthene dye, triarylmethane dye, coumarine dye, anthraquinone dye, azo dyes and tetraazatetradecane porphyrin dyestuff, particularly preferably Xanthene dye, azo dyes.
In these, preferably the sulfonamide compound of C.I. acid reds 289, the quaternary ammonium salt of C.I. acid reds 289, C.I. acid violets 102 sulfonamide compound or the quaternary ammonium salt of C.I. acid violets 102.
As xanthene dye, in addition to foregoing illustrative compound, for example, C.I. CI 45430s can be also included (following Omit statement " C.I. acid reds ", only record sequence number, other similarly), 52,87,92,94,388, C.I. acid violets 9,30, C.I. alkali red 1:1 (rhodamine 6G), 2,3,4,8, C.I. alkali red 1:1s 0 (rhodamine B), 11, C.I. alkaline purple 1s 0,11,25, C.I. solvent red 218, C.I. mordant rouges 27, C.I. active reds 36 (rose red b), Sulfo rhodamine G, Japanese Unexamined Patent Publication 2010- Xanthene dye described in No. 4492760 publication of xanthene dye and patent described in No. 32999 publications etc..
Xanthene dye is more preferably the compound (hereinafter also referred to compound (a1-1)) represented by following formula (a1-1). Compound (a1-1) can be its dynamic isomer.
[in formula (a1-1), R1~R4Represent independently of each other hydrogen atom, can have substituent carbon number 1~20 1 valency Saturated hydrocarbyl or can have substituent carbon number 6~10 1 valency aromatic hydrocarbyl, contained methylene in the saturated hydrocarbyl Base (- CH2-) can be by-O- ,-CO- or-NR11- replace.R1And R2The ring comprising nitrogen-atoms, R can be formed together3And R4Can shape together Into the ring comprising nitrogen-atoms.
R1~R4In, adjacent methylene will not be replaced by oxygen atom simultaneously, in addition, the methylene of the end of alkyl Oxygen atom will not be replaced by.
R5Expression-OH ,-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8Or-SO2NR9R10。
R6And R7The alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.
M represents 0~5 integer.When m is more than 2, multiple R5Can be with identical, also can be different.
A represents 0 or 1 integer.
X represents halogen atom.
Z+Represent+N(R11)4、Na+Or K+, 4 R11Can be with identical, also can be different.
R8Represent that hydrogen atom contained in the saturated hydrocarbyl of 1 valency of carbon number 1~20, the saturated hydrocarbyl can be by halogen atom Substitution.
R9And R10Hydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, should Contained-CH in saturated hydrocarbyl2- can be by-O- ,-CO- ,-NH- or-NR8- replace, R9And R10It can be combined with each other and be formed containing nitrogen The heterocycle of 3~10 yuan of rings of atom.
R11Represent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.]
In addition, as xanthene dye, it is also preferred that the compound (hereinafter sometimes referred to " compound represented by formula (a1-2) (a1-2)”).Compound (a1-2) can be its dynamic isomer.
[in formula (a1-2), R21And R22The saturated hydrocarbyl of 1 valency of carbon number 1~10, the R are represented independently of each other21、R22It is full It can be replaced with hydrogen atom contained in alkyl by the aromatic hydrocarbyl or halogen atom of carbon number 6~10, in the aromatic hydrocarbyl Contained hydrogen atom can be replaced by the alkoxy of carbon number 1~3, above-mentioned R21、R22Saturated hydrocarbyl in contained-CH2- can be with By-O- ,-CO- or-NR11- replace.
R23And R24The alkyl, the alkyl alkylthio base of carbon number 1~4 or carbon number 1~4 of carbon number 1~4 are represented independently of each other Alkyl sulphonyl.
R21And R23The ring containing nitrogen-atoms, R can be formed together22And R24The ring containing nitrogen-atoms can be formed together.
P and q represent 0~5 integer independently of each other.When p is more than 2, multiple R23Can be with identical, also can be different, q is 2 During the above, multiple R24Can be with identical, also can be different.
R11Represent implication same as described above.]
It is used as R21And R22In carbon number 1~10 1 valency saturated hydrocarbyl, R can be included8In group in carbon number 1~10 Group.
As the aromatic hydrocarbyl for the carbon number 6~10 that can have as substituent, it can include and R1In group it is identical Group.
As the alkoxy of carbon number 1~3, such as can include methoxyl group, ethyoxyl, propoxyl group.
R21And R22It is preferred that being independently of one another the saturated hydrocarbyl of 1 valency of carbon number 1~3.
It is used as R23And R24In carbon number 1~4 alkyl, methyl, ethyl, propyl group, butyl, isopropyl, isobutyl can be included Base, sec-butyl, tert-butyl group etc..
It is used as R23And R24In carbon number 1~4 alkyl alkylthio base, methylsulfanyl, Ethylsulfanyl, third can be included Base sulfanyl, butyl sulfanyl and isopropyl sulfanyl etc..
It is used as R23And R24In carbon number 1~4 alkyl sulphonyl, methyl sulphonyl, ethylsulfonyl, third can be included Base sulfonyl, butyl sulfonyl and isopropelsulfonyl etc..
It is used as R23And R24, the preferably alkyl of carbon number 1~4, more preferably methyl, ethyl, further preferred methyl.
It is used as p and q, preferably 0~2 integer, preferably 1 or 2.
Triarylmethane dye is preferably the chemical combination for including the structure that a carbon atom is incorporated into 3 aromatic hydrocarbyls The dyestuff of thing.As triarylmethane dye, for example, it can include C.I. solvent blues 2,4,5,43,124；C.I. alkaline purple 3, 14、25；C.I. triarylmethane dye described in No. 4492760 publications of alkali blue 1,5,7,11,26 and Japanese Patent No. etc..
Coumarine dye is the dyestuff of the compound included in intramolecular with coumarin skeleton.As coumarine dye, Such as C.I. Indian yellows 227,250 can be included；C.I. disperse yellow 82,184；C.I. solvent orange 112；C.I. solvent yellow 16 0, 172；Coumarine dye described in No. 1299948 publications of Japanese Patent No. etc..
As anthraquinone dye, can including C.I. solvent yellows 117, (statement " C.I. solvent yellows " omitted below, only records sequence Number), 163,167,189,
C.I. solvent orange 77,86,
C.I. solvent red 111,143,145,146,150,151,155,168,169,172,175,181,207,222, 227、230、245、247、
C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60,
C.I. solvent blue 19 4,18,35,36,45,58,59,59：1、63、68、69、78、79、83、94、97、98、100、 101、102、104、105、111、112、122、128、132、136、139、
C.I. solvent green 3,28,29,32,33,
C.I. acid red 80,
C.I. ACID GREEN 25,27,28,41,
C.I. acid violet 34,
C.I. acid blue 25,27,40,45,78,80,112,
C.I. disperse yellow 51,
C.I. disperse violet 26,27,
C.I. disperse blue 1,14,56,60,
C.I. directly indigo plant 40,
C.I. mordant rouge 3,11,
C.I. mordant dyeing indigo plant 8 etc..
Tetraazatetradecane porphyrin dyestuff is the compound in intramolecular with tetraazatetradecane porphyrin skeleton.In addition, tetraazatetradecane porphyrin contaminates , can be with arbitrary cation or anion forming salt in the case of expecting for acid dyes or basic-dyeable fibre.
As other dyestuffs, azo dyes, thiazole dye, oxazine dyes, phthalocyanine dye, quinophthalone dyestuff can be used Deng each using known dyestuff.
As azo dyes, can for example including C.I. directly Huangs, (statement " C.I. is directly yellow " omitted below, only records sequence Number) 2,33,34,35,39,50,69,70,71,86,93,94,95,98,102,109,129,136,141；
C.I. direct orange 41,46,56,61,64,70,96,97,106,107；
C.I. directly red 79,82,83,84,97,98,99,106,107,172,173,176,177,179,181,182, 204、207、211、213、218、221、222、232、233、243、246、250；
C.I. directly purple 47,52,54,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104；
C.I. directly indigo plant 51,57,71,81,84,85,90,93,94,95,98,100,101,113,149,150,153, 160、162、163、164、166、167、170、172、188、192、193、194、196、198、200、207、209、210、212、 213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、 260、268、274、275；
C.I. direct green 27,34,37,65,67,68,69,72,77,79,82；
C.I. azogeramine, 3,4,6,8,11,12,14,18,26,27,33,37,53,57,88,106,108,111,114, 131、137、138、151、154、158、159、173、184、186、215、257、266、296、337；
C.I. acid orange 7,10,12,19,20,22,28,30,52,56,74,127；
C.I. acid violet 11,56,58；
C.I. Indian yellow 1,17,18,23,25,36,38,42,44,54,59,72,78,151；
C.I. acid brown 2,4,13,248；
C.I. acid blue 92,102,113,117；
C.I. alkali red 1:1 7,22,23,25,29,30,38,39,46,46：1、82；
C.I. alkaline orange 2,24,25；
C.I. alkaline purple 18；
C.I. basic yellow 15,24,25,32,36,41,73,80；
C.I. bismarck brown 1；
C.I. alkali blue 41,54,64,66,67,129 etc..
As metallic complex salt azo dyes, C.I. solvent reds 125,130 can be included；C.I. solvent yellow 21 and Japan are special Open compound that 2010-170116 publications or Japanese Unexamined Patent Publication 2011-215572 publications are recorded etc..
As thiazole dye, C.I. directly Huang 54, C.I. basic yellows 1 etc. can be included.
Zuo Wei oxazine dyes, can include C.I. directly indigo plants 97,99,106,107,108,109,190,293 etc..
As phthalocyanine dye, C.I. directly indigo plant 86,87,189,199, C.I. acid blues 249, C.I. alkali blues can be included 3 etc..
As quinophthalone dyestuff, C.I. quinoline yellows, C.I. disperse yellows 143 etc. can be included.
As cyanine dyes, copper phthalocyanine (C.I.74160) etc. can be included.
As quinoneimine dye, C.I. alkali blue 3s, C.I. alkali blues 9 etc. can be included.
As methine dyes, C.I. Basic Red 13s, 14 can be included；C.I. alkaline orange 21；C.I. Basic Violet16,39； C.I. basic yellow 11,13,21,23,28 etc..
As quinoline dye, C.I. solvent yellow 33s, C.I. quinoline yellows, C.I. dispersion yellow 64s etc. can be included.
As nitro dye, C.I. Indian yellows 1, C.I. acid oranges 3, C.I. Disperse Yellow 42s etc. can be included.
As azine dye, C.I. acid blues 59,102 etc. can be included.
As bipseudoindoxyl dye, C.I. Acid Blue 7s 4 etc. can be included.
Color dispersion liquid
When manufacturing the colored curable resin composition of the present invention, for compound (Aa), preferably make it in a solvent Dissolving disperses, mixes and prepare color dispersion liquid.By by color dispersion liquid and resin glue (B), polymerizable compound (C), polymerization initiator (D) etc. mixes and prepares colored curable resin composition, so as to further improve by the coloring The heat resistance of the colour filter of hardening resin composition formation.
As solvent, as long as the solvent that can be used as the solvent (E) of colored curable resin composition, then can be with Use any solvent.Solvent is such as ether-ether solvent, it is highly preferred that can include aklylene glycol or PAG One etherification of hydroxyl groups, the solvent by remaining hydroxy esterification, such as propylene glycol monomethyl ether, propane diols list ethyl It is ether acetic acid ester, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, two sweet Alcohol list monoethyl ether acetate, diethylene glycol monobutyl ehter acetic acid esters, dipropylene glycol methyl ether acetic acid esters etc..These can be used alone or Person is comprising a variety of.
In color dispersion liquid, relative to the mass parts of compound (Aa) 1, the content of solvent is, for example, 1~50 mass parts, preferably For 2~30 mass parts, more preferably 3~10 mass parts.
When the compound (Aa) is scattered in solvent, prepared color dispersion liquid, dispersant is preferably used.It is used as dispersant, energy Enough using the known pigment point of cation system, anion system, nonionic system, both sexes, Polyester, many amine systems, acrylic acid series etc. Powder.These pigment dispersing agents may be used alone, or two or more kinds may be used in combination.As pigment dispersing agent, with commodity Name is represented, can include KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), Off ロ ー レ Application (common prosperity society chemistry (strain) manufacture), ソ Le ス パ ー ス (ゼ ネ カ (strain) manufactures), EFKA (BASF AG's manufacture), ア ジ ス パ ー (aginomoto Off ァ イ Application テ Network ノ (strain) Manufacture), Disperbyk (manufacture of PVC ッ Network ケ ミ ー companies) etc..
In the color dispersion liquid, the content of dispersant, relative to the mass parts of compound (Aa) 100, for example, 1~1000 matter Measure part, particularly preferably preferably 3~100 mass parts, more preferably 5~50 mass parts, 10~30 mass parts.
Color dispersion liquid can include part or all of dyestuff (Ab) in advance, preferably comprising whole.Relative to chemical combination The amount of dyestuff (Ab) in the mass parts of thing (Aa) 100, color dispersion liquid is, for example, 0.1~20 mass parts, preferably 0.5~10 matter Measure part, more preferably 1~5 mass parts.
Make that compound (Aa) is disperseed in a solvent and in the case of preparing color dispersion liquid, color dispersion liquid can be included in advance Part or all of the resin glue (B) contained in colored curable resin composition, preferably comprising a part.Pass through Contain resin glue (B) in advance, can further improve dispersion stabilization when colored curable resin composition is made. The content of resin glue (B) in color dispersion liquid, relative to the mass parts of compound (Aa) 100, for example, 1~300 mass parts, Preferably 10~100 mass parts, more preferably 20~70 mass parts.
Colouring agent (A) can further include pigment (Ac) in addition to compound (Aa) and dyestuff (Ab).As pigment, The pigment that pigment is categorized as in colour index (The Society of Dyers and Colourists publication) can for example be included (but, different from compound (Aa)), can illustrate following pigment.
Viridine green：C.I. pigment Green 7,36,58 etc.
Yellow uitramarine：C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109, 110th, 117,125,128,129,137,138,139,147,148,150,153,154,166,173,185,194,214 etc.
Orange pigment：C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73 etc.
Red pigment：C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192, 209th, 215,216,224,242,254,255,264,265 etc.
Green pigment：C.I. pigment blue 15,15：3、15：4、15：6th, 60 etc.
Violet pigment：C.I. pigment violet 1,19,23,29,32,36,38 etc.
For these pigment, for colors, a kind of pigment or a variety of pigment can be used, also can be by assorted pigment combination.
Pigment can implement rosin processing, use pigment derivative for having imported acidic groups or basic group etc. as needed Surface treatment, using high-molecular compound etc. to the grafting processing of surface of pigments, using the particulate of sulfuric acid particles method etc. Change processing or the cleaning treatment for the use organic solvent, the water that remove impurity etc., the ion using ionic impurity are handed over Change removing processing of method etc. etc..The particle diameter of pigment is preferably substantially homogeneous.For pigment, by being carried out containing pigment dispersing agent Decentralized processing, so as to be formed in the dispersible pigment dispersion of state uniformly dispersing in pigment dispersing agent solution.For pigment, Decentralized processing each can be individually carried out, also a variety of mixing decentralized processing can be subjected to.
As pigment dispersing agent, surfactant etc. can be included, can for cation system, anion system, nonionic system, Any surfactant of both sexes.Specifically, the surfactant of Polyester, many amine systems, acrylic acid series etc. can be included Deng.Wherein, particularly preferred acrylic acid series surfactant.These pigment dispersing agents can be used alone or by two kinds of combination of the above Use.As pigment dispersing agent, represented with trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), フ ロ ー レ Application can be included (common prosperity society chemistry (strain) manufacture), ソ Le ス パ ー ス (registration mark) (ゼ ネ カ (strain) manufactures), EFKA (registration mark) (BASF AG's manufacture), ア ジ ス パ ー (registration mark) (aginomoto Off ァ イ Application テ Network ノ (strain) manufactures), Disperbyk (registration mark) (manufacture of PVC ッ Network ケ ミ ー companies) etc..
In the case of using pigment dispersing agent, relative to the mass parts of pigment 100, its usage amount be preferably 200 mass parts with Under, below more preferably 180 mass parts, below more preferably 160 mass parts, particularly preferably 0 mass parts.If pigment The usage amount of dispersant is in above-mentioned scope, in the case of using pigment of more than two kinds, scattered with what is be more uniformly distributed The tendency of the dispersible pigment dispersion of state.
Relative to the total amount of solid constituent, the containing ratio of the colouring agent (A) in colored curable resin composition is usually More than 10 mass % and below 70 mass %, preferably more than 15 mass % and below 60 mass %, more preferably 20 mass % Above and below 55 mass %, particularly preferably more than 25 mass % and below 50 mass %.If above-claimed cpd (Aa) Containing ratio is in above-mentioned scope, it is easier to obtain desired light splitting, colour saturation.It should be noted that in this specification " solid into The total amount divided " refers to the total amount of the composition after solvent is removed from the colored curable resin composition of the present invention.Solid The total amount of composition and relative to solid constituent total amount each composition content such as can use liquid chromatogram, gas-chromatography public affairs The analysis means known are determined.
The mass ratio (dyestuff (Ab)/compound (Aa)) of dyestuff (Ab) and compound (Aa) is preferably more than 0.001 and 0.5 Hereinafter, more preferably more than 0.005 and less than 0.4, more preferably more than 0.01 and less than 0.3.
In the case of comprising pigment (Ac), relative to above-mentioned colouring agent (A) total amount, the containing ratio of pigment (Ac) is preferably Below 70 mass %, more preferably below 60 mass %, more preferably below 50 mass %, particularly preferably 0 mass %.
＜ resin glues (B) ＞
Contained resin glue (B) is preferably alkali soluble resin in the colored curable resin composition of the present invention, More preferably there is the addition polymerization from least one construction unit selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides Thing.As such resin, following resins [K1]~[K6] can be included.
Resin [K1]：Monomer (a) selected from least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides is (following to be sometimes referred to as For " (a) ") and ring-type ether structure and the monomer (b) (hereinafter sometimes referred to " (b) ") of ethylenic unsaturated bond with carbon number 2~4 Copolymer
Resin [K2]：(a), (b) and can be with the monomer (c) (but, different from (a) and (b)) of (a) copolymerization (below sometimes Copolymer referred to as " (c) ")
Resin [K3]：(a) with the copolymer of (c)
Resin [K4]：By making (b) and resin obtained from the copolymer reaction of (a) and (c)
Resin [K5]：By making (a) and resin obtained from the copolymer reaction of (b) and (c)
Resin [K6]：By making (a) and (b) and (c) copolymer reaction and then making to set obtained from carboxylic acid anhydride reactant Fat.
As (a), acrylic acid, methacrylic acid, crotonic acid and o-, m-, p- vinyl benzoic acid etc. can be included Unsaturated monocarboxylic；
The adjacent benzene two of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid and 1,4- The unsaturated dicarboxylics such as cyclohexene dicarboxylic acid；
Methyl -5- ENB -2,3- dicarboxylic acids, bicyclic [2.2.1] hept-2-ene" of 5- carboxyls, 5,6- dicarboxyls are bicyclic [2.2.1] hept-2-ene", 5- carboxyl -5- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] the hept- 2- of 5- carboxyl -5- ethyls Alkene, 5- carboxyl -6- methyl bicycles [2.2.1] hept-2-ene"s and bicyclic [2.2.1] hept-2-ene" of 5- carboxyl -6- ethyls etc. contain carboxyl Bicyclic unsaturated compound；
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- vinylphthalic acids acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride and 5, Unsaturated dicarboxylic acid anhydrides such as bicyclic [2.2.1] the hept-2-ene" acid anhydride of 6- dicarboxyls etc..
In addition, mono succinate [2- (methyl) acryloyl-oxyethyl] ester and phthalic acid list [2- (methyl) can be used Acryloyl-oxyethyl] more than 2 yuan of the polybasic carboxylic acid such as ester single [(methyl) acryloxyalkyl] esters of unsaturation；α- Unsaturated esters of acrylic acid containing hydroxyl and carboxyl in same molecule such as (hydroxymethyl) acrylic acid etc..
In these, monomer (a) is preferably unsaturated monocarboxylic, more preferably acrylic acid and methacrylic acid.
It should be noted that in this specification, statement " (methyl) acrylic acid " is represented in acrylic acid and methacrylic acid It is at least one kind of.State " (methyl) acrylate " etc. similarly.
(b) refer to the ring-type ether structure with carbon number 2~4 (for example, selected from oxirane ring, oxetanes ring and four It is at least one kind of in hydrogen furan nucleus) and ethylenic unsaturated bond polymerizable compound.(b) it is preferably the ring-type with carbon number 2~4 The monomer of ether structure and (methyl) acryloxy.
As (b), the monomer (b1) with epoxy ethyl and ethylenic unsaturated bond can be included (hereinafter sometimes referred to " (b1) "), the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanylmethoxy and ethylenic unsaturated bond and with tetrahydrochysene The monomer (b3) (hereinafter sometimes referred to " (b3) ") of furyl and ethylenic unsaturated bond.
As (b1), the structure that the unsaturated aliphatic hydrocarbon with straight-chain or branch's chain state is at least partially epoxidized can be included Monomer (the b1- of monomer (b1-1) (hereinafter sometimes referred to " (b1-1) ") and the structure being at least partially epoxidized with ester ring type unsaturated hydrocarbons 2) (hereinafter sometimes referred to " (b1-2) ").
As (b1-1), the monomer preferably with glycidyl and ethylenic unsaturated bond.As (b1-1), specifically, (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-second can be included Base ethylene oxidic ester, glycidyl vinyl ether, o- vinylbenzyl glycidyl base ether, m- vinyl benzyl shrink sweet Oleyl ether, p- vinylbenzyl glycidyl base ether, Alpha-Methyl-o- vinylbenzyl glycidyl base ether, Alpha-Methyl-m- Double (the glycidoxypropyl first of vinylbenzyl glycidyl base ether, Alpha-Methyl-p- vinylbenzyl glycidyl base ether, 2,3- Base) styrene, double (glycidoxypropyl methyl) styrene of 2,4-, 2,5- double (glycidoxypropyl methyl) styrene, 2,6- Double (glycidoxypropyl methyl) styrene, 2,3,4- tri- (glycidoxypropyl methyl) styrene, (glycidols of 2,3,5- tri- Epoxide methyl) styrene, 2,3,6- tri- (glycidoxypropyl methyl) styrene, 3,4,5- tri- (glycidoxypropyl methyl) benzene Ethene and 2,4,6- tri- (glycidoxypropyl methyl) styrene.
As (b1-2), can include vinylcyclohexene monoxide, 1,2- epoxy -4- vinyl cyclohexanes (for example, セ ロ キ サ イ De (registration mark) 2000；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylate (examples Such as, サ イ Network ロ マ ー (registration mark) A400；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates (for example, サ イ Network ロ マ ー M100；(strain) Daicel manufacture), by formula (1) represent compound and by formula (2) represent chemical combination Thing.
[in formula (1) and formula (2), RaAnd RbInstitute in the alkyl of hydrogen atom or carbon number 1~4, the alkyl is represented independently of each other The hydrogen atom contained can be optionally substituted by a hydroxyl group.
XaAnd XbSingly-bound, *-R are represented independently of each otherC-, *-RC- O-, *-RC- S- or *-RC-NH-。RCRepresent carbon number 1~6 alkylidene.* the bonding end with O is represented.]
As the compound represented by formula (1), the compound represented by formula (1-1)~formula (1-15) can be included, wherein, It can preferably include by formula (1-1), formula (1-3), formula (1-5), formula (1-7), formula (1-9) and formula (1-11)~formula (1-15) table The compound shown, can more preferably include the compound represented by formula (1-1), formula (1-7), formula (1-9) and formula (1-15).
As the compound represented by formula (2), the compound represented by formula (2-1)~formula (2-15) can be included, wherein, It can preferably include by formula (2-1), formula (2-3), formula (2-5), formula (2-7), formula (2-9) and formula (2-11)~formula (2-15) table The compound shown, can more preferably include the compound represented by formula (2-1), formula (2-7), formula (2-9) and formula (2-15).
The compound represented by formula (1) and the compound represented by formula (2) can each be used alone, also can be by by formula (1) compound represented is used in combination with the compound represented by formula (2).In the case of these and use, the chemical combination represented by formula (1) Ratio (the compound represented by formula (1) of thing and the compound represented by formula (2)：By formula (2) represent compound) with mole Benchmark meter, preferably 5：95~95：5, more preferably 10：90~90：10, more preferably 20：80~80：20.
As (b2), the monomer more preferably with oxetanylmethoxy He (methyl) acryloxy.
As (b3), the monomer more preferably with tetrahydrofuran base He (methyl) acryloxy.
In terms of it can further improve the reliability of heat resistance, the chemical-resistant of obtained colour filter etc., (b) is excellent Elect (b1) as, in terms of the excellent storage stability of colored curable resin composition, (b1) is preferably (b1-2)
As (c), following (c1)~(c6) monomer etc. can be used.
As (methyl) acrylate of (c1) containing hydroxyl, (methyl) acrylic acid 2- hydroxy methyls, (first can be included Base) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, 1,3 butylene glycol (methyl) acrylate, 1,4- butanediols (methyl) acrylate, 1,6-HD (methyl) acrylate, 3- methyl pentanediols (methyl) acrylate etc..
(methyl) acrylate containing hydroxyl is preferably (methyl) dihydroxypropyl alkane of the alkyl with carbon number 1~10 Base ester, more preferably contains hydroxyl with carbon number 1~8, more preferably carbon number 1~6, the particularly preferably alkyl of carbon number 1~4 (methyl) acrylate.
Wherein, and specifically, it is preferable to be (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (first Base) acrylic acid 4- hydroxybutyls, more preferably (methyl) acrylic acid 2- hydroxy methacrylates.
As (c2) di carbonyl imide compound, N-phenylmaleimide, N- tolylmaleimides can be included Deng the di carbonyl imide with aromatic hydrocarbyl, N- N-cyclohexylmaleimides, N- cycloheptylmaleimides, N- cyclooctyl horses Come acid imide, N- cyclo-dodecyl maleimides etc. with the di carbonyl imide of alicyclic type hydrocarbon, N- benzyl maleimides, N- phenethyl maleimides etc. have di carbonyl imide, the N- succinimide base -3- maleimidobenzoyls of aralkyl Salt, N- succinimide base -4- maleimidobutyrates salt, N- succinimide base -6- maleimidohexanoic acids salt and N- ambers Amber acylimino -3- maleimidopropionic acid salt etc. has the di carbonyl imide of succinimide base etc., N- (9- acridinyls) horse Carry out di carbonyl imide with annelated heterocycles base such as acid imide etc..
The monomer of above-mentioned di carbonyl imide derivative is preferably the N substituted maleimide amine of the alkyl with carbon number 4~20. Contained hydrogen atom can be by amino, carbon number in alkyl in the N substituted maleimide amine of the above-mentioned alkyl with carbon number 4~20 1~5 alkoxy, phenyl amino, halogen atom or hydroxyl etc. replace.
As the alkyl of above-mentioned carbon number 4~20, alicyclic type hydrocarbon, the fragrance of carbon number 6~20 of carbon number 4~20 can be included The aralkyl of race's alkyl and carbon number 7~20.As the group for replacing hydrogen atom contained in above-mentioned alkyl, amber can be included Acylimino etc..
The monomer of di carbonyl imide derivative is preferably the N substituted maleimides of the alicyclic type hydrocarbon with carbon number 4~20 Amine, can specifically include N- N-cyclohexylmaleimides, N- cycloheptylmaleimides, N- cyclooctyls maleimide and N- Cyclo-dodecyl maleimide, can more preferably include N- N-cyclohexylmaleimides.
As (c3) (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be included Base) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring penta Ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyls, the ring [5.2.1.0 of (methyl) acrylic acid three2,6] last of the ten Heavenly stems Alkane -8- base esters (in the technical field, as trivial name, are referred to as " the bicyclic pentyl ester of (methyl) acrylic acid ".In addition, sometimes referred to as " (methyl) acrylic acid tricyclodecyl "), the ring [5.2.1.0 of (methyl) acrylic acid three2,6] decene -8- base esters (in the technical field, As trivial name, referred to as " (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate "), the bicyclic amoxy ethyl ester of (methyl) acrylic acid, (methyl) third Olefin(e) acid isobornyl thiocyanoacetate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (first Base) phenyl acrylate, (methyl) acrylic acid naphthalene ester and (methyl) benzyl acrylate etc..
As (c4) dicarboxylic diester, diethyl maleate, diethyl fumarate and diethyl itaconate etc. can be included.
As (c5) bicyclic unsaturated compound, bicyclic [2.2.1] hept-2-ene", 5- methyl bicycles [2.2.1] can be included Bicyclic [2.2.1] hept-2-ene" of hept-2-ene", 5- ethyls, bicyclic [2.2.1] hept-2-ene" of 5- hydroxyls, 5- hydroxymethyls are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- (2 '-hydroxyethyl), bicyclic [2.2.1] hept-2-ene" of 5- methoxyl groups, Bicyclic [2.2.1] hept-2-ene" of 5- ethyoxyls, bicyclic [2.2.1] hept-2-ene" of 5,6- dihydroxy, 5,6- bis- (hydroxymethyl) are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5,6- bis- (2 '-hydroxyethyl), 5,6- dimethoxys are bicyclic [2.2.1] Bicyclic [2.2.1] hept-2-ene" of hept-2-ene", 5,6- diethoxies, bicyclic [2.2.1] hept-2-ene" of 5- hydroxy-5-methyl bases, 5- hydroxyls Bicyclic [2.2.1] hept-2-ene" of base -5- ethyls, 5- hydroxymethyl -5- methyl bicycles [2.2.1] hept-2-ene", 5- t-butoxy carbonyls Bicyclic [2.2.1] hept-2-ene" of base, bicyclic [2.2.1] hept-2-ene" of 5- cyclohexyloxy carbonyls, 5- phenyloxycarbonyls are bicyclic [2.2.1] Double (t-butoxy carbonyl) bicyclic [2.2.1] hept-2-ene"s of hept-2-ene", 5,6- and 5,6- double (cyclohexyloxy carbonyls) are bicyclic [2.2.1] hept-2-ene" etc..
(c6) styrene, α-methylstyrene, m- methyl styrene, p-methylstyrene, vinyl first can be included The aromatic compound containing vinyl such as benzene and p-methoxystyrene；Acrylonitrile, methacrylonitrile etc. contain vinyl Nitrile；The halogenated hydrocarbons such as vinyl chloride and vinylidene chloride；The acid amides containing vinyl such as acrylamide and Methacrylamide；Vinyl acetate The esters such as ester；Diene of 1,3- butadiene, isoprene and 2,3- dimethyl -1,3- butadiene etc..
In these, from the viewpoint of copolyreaction and heat resistance, it can preferably include (methyl) containing hydroxyl Acrylate and di carbonyl imide compound, it is highly preferred that (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) propylene can be included Sour 2- hydroxy propyl esters, N-phenylmaleimide, N- N-cyclohexylmaleimides and N- benzyl maleimides.
Construction unit with ethylenic unsaturated bond is preferably the construction unit with (methyl) acryloyl group.With so Construction unit resin can by make to have from (a), the polymer of the construction unit of (b) with can be with (a), (b) The monomer addition of the group and ethylenic unsaturated bond of the radical reaction having and obtain.
As such construction unit, (methyl) glycidyl acrylate addition of sening as an envoy to can be enumerated in (methyl) acrylic acid The construction unit of unit, make the 2- hydroxy methacrylates addition of (methyl) acrylic acid in maleic anhydride units construction unit, Make the addition of (methyl) acrylic acid in construction unit of (methyl) glycidyl acrylate unit etc..In addition, these structures In the case that unit has hydroxyl, as the construction unit with ethylenic unsaturated bond, can also include further makes carboxylic acid anhydrides The construction unit of addition.
Polymer with the construction unit from (a) for example can be by the presence of polymerization initiator, in solvent In the monomer of construction unit of composition polymer is polymerize and is manufactured.Special limit is had no to polymerization initiator and solvent etc. It is fixed, polymerization initiator and solvent usually used in the field can be used.For example, as polymerization initiator, idol can be included Nitrogen compound (2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4- methyl pentane nitriles) etc.), organic peroxide (peroxidating Benzoyl etc.), as solvent, as long as each monomer is dissolved, it is used as the molten of colored curable resin composition of the invention Agent (E), can include solvent described later etc..
Further, obtained polymer can directly use reacted solution, it is possible to use the solution of concentration or dilution, The product taken out using methods such as reprecipitations as solid (powder) can also be used.Especially, in the polymerization as solvent, , can be by reacted solution directly in this hair by using solvent contained in the colored curable resin composition of the present invention Used in the preparation of bright colored curable resin composition, therefore, it is possible to simplify the colored curable resin composition of the present invention Manufacturing process.
As needed, catalysts (such as three (the dimethylamino first of carboxylic acid or carboxylic acid anhydrides and cyclic ether can be used Base) phenol etc.) and polymerization inhibitor (such as quinhydrones) etc..
As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- can be included Vinylphthalic acid acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl four Hydrogen phthalic anhydride and bicyclic [2.2.1] the hept-2-ene" acid anhydride of 5,6- dicarboxyls etc..
As resin glue (B), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates/(methyl) acrylic acid can be used Copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three2,6] resin [K1] such as last of the ten Heavenly stems ester/(methyl) acrylic copolymer； (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid shrink sweet Grease/styrene/(methyl) acrylic copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three2,6] last of the ten Heavenly stems ester/(methyl) Acrylic acid/N- N-cyclohexylmaleimides copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three2,6] last of the ten Heavenly stems ester/(first Base) acrylic acid/vinyl toluene copolymer, 3- methyl -3- (methyl) acryloyloxymethyls oxetanes/(methyl) propylene The resins such as acid/styrol copolymer [K2]；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) third The resins such as olefin(e) acid copolymer, (methyl) benzyl acrylate/(methyl) acrylic acid tricyclodecyl/(methyl) acrylic copolymer [K3]；Make the addition of (methyl) glycidyl acrylate in (methyl) benzyl acrylate/(methyl) acrylic copolymer resin, Make the addition of (methyl) glycidyl acrylate in (methyl) acrylic acid tricyclodecyl/styrene/(methyl) acrylic copolymer Resin, make the addition of (methyl) glycidyl acrylate in (methyl) acrylic acid tricyclodecyl/(methyl) benzyl acrylate/ The resin such as resin of (methyl) acrylic copolymer [K4]；Make (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl/(first Base) glycidyl acrylate copolymer reaction resin, make (methyl) acrylic acid and the ring last of the ten Heavenly stems of (methyl) acrylic acid three The resins [K5] such as the resin of copolymer reaction of ester/styrene/(methyl) glycidyl acrylate；Make (methyl) propylene Acid and the copolymer reaction of (methyl) acrylic acid tricyclodecyl/(methyl) glycidyl acrylate, make tetrahydrophthalic acid Acid anhydride further with the resin [K6] such as the resin of the resin reaction of gained.These resins can be used alone, also can be by 2 kinds Combination of the above.
Wherein, resin glue (B) is preferably resin [K2], more preferably with from from unsaturated carboxylic acid and unsaturation The construction unit of at least one kind of monomer (a) selected in carboxylic acid anhydrides, from the list with ethylenic unsaturated bond and ring-type ether structure The construction unit of body (b), the construction unit from (methyl) acrylate monomer (c1) containing hydroxyl and sub- from dicarbapentaborane The copolymer of the construction unit of the monomer (c2) of amine derivative, more preferably has since acrylic acid and methacrylic acid The construction unit of at least one kind of monomer (a) of middle selection, come since the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three2,6] The construction unit of at least one kind of monomer (b) selected in last of the ten Heavenly stems ester and (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates, come since The structure of at least one kind of monomer (c1) selected in (methyl) acrylic acid 2- hydroxy methacrylates and (methyl) acrylic acid 2- hydroxy propyl esters Unit and come since selected in N-phenylmaleimide, N- N-cyclohexylmaleimides and N- benzyl maleimides to The copolymer of the construction unit of few a kind monomer (c2).
In resin [K2], for the containing ratio of the construction unit from each monomer, the whole of resin [K2] is being constituted Construction unit it is total in, be preferred from the construction unit of (a) for 2~45 moles of %, the construction unit from (b) is 2~65 Mole %, the construction unit from (c) is 1~95 mole of %, and the construction unit more preferably from (a) is 5~40 moles of %, is come Construction unit from (b) is 5~60 moles of %, and the construction unit from (c) is 10~80 moles of %.
(a)~(c) it is respective in contained monomer can be a kind, or two or more.(c) be preferably selected from (c1)~ (c6) two or more in, more preferably two or more in (c1)~(c3), more preferably (c1) and (c2).
The containing ratio of construction unit from (c1), the entire infrastructure unit from (c) it is total in, preferably 1~ 60 moles of %, more preferably 10~50 moles %, more preferably 20~40 moles %.
The containing ratio of construction unit from (c2), the entire infrastructure unit from (c) it is total in, preferably 30~ 90 moles of %, more preferably 40~80 moles %, more preferably 50~70 moles %.
In the case that resin glue of more than two kinds (B) is combined, preferred resin [K1] and/or resin [K2] and resin The combination of [K4]~resin [K6], more preferably resin [K1] and/or resin [K2] and the combination of resin [K4].
The weight average molecular weight of the polystyrene conversion of resin glue (B) is preferably more than 3000 and less than 100000, more Preferably more than 4000 and less than 100000, more preferably more than 5000 and less than 80000, particularly preferably more than 6000 And less than 50000, especially preferably more than 7500 and less than 40000.If molecular weight is in above-mentioned scope, hard with film Degree is improved, residual film ratio is also high, unexposed portion for inclining that the favorable solubility of developer solution, the resolution ratio of colored pattern are improved To.The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin glue (B) is preferably 1.1~6, more excellent Elect 1.2~4, more preferably 1.3~3 as.
The acid number (solid constituent conversion) of resin glue (B) is preferably 30~200mg-KOH/g, more preferably 35mg- More than KOH/g, more preferably more than 40mg-KOH/g, particularly preferably below 180mg-KOH/g, especially preferably Below 150mg-KOH/g.What acid number was determined for the amount (mg) as the potassium hydroxide needed for neutralizing resin glue (B) 1g Value, for example, can use potassium hydroxide aqueous solution to be titrated and obtained.
Total containing ratio of resin glue (B), relative to the total amount of solid constituent, preferably 10~65 mass %, More preferably 15~60 mass %, more preferably 20~55 mass %, particularly preferably 25~50 mass %.If bonded The containing ratio of agent resin (B) is in above-mentioned scope, and colored pattern is formed easily, resolution ratio and residual film ratio with colored pattern The tendency of raising.
＜ polymerizable compounds (C) ＞
Polymerizable compound (C) is the change that can utilize the living radical produced by polymerization initiator and/or acid polymerization Compound, can include such as polymerizable compound with ethylenic unsaturated bond, and can preferably include has (methyl) propylene The compound of acrylate structure.Polymerizable compound (C) is preferably the polymerism chemical combination with the ethylenic unsaturated bond of more than 3 Thing, the more preferably polymerizable compound with 5~6 ethylenic unsaturated bonds.
As the polymerizable compound with 1 ethylenic unsaturated bond, can include nonyl phenyl carbitol acrylate, Acrylic acid 2- hydroxyl -3- phenoxy-propyls, 2- ethylhexyl carbitols acrylate, acrylic acid 2- hydroxy methacrylates, N- vinyl Pyrrolidones, above-mentioned (a), (b) and (c).
As the polymerizable compound with 2 ethylenic unsaturated bonds, 1,6- hexylene glycols two (methyl) propylene can be included Acid esters, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, Double (acryloyl-oxyethyl) ethers and 3- methyl pentanediols two (methyl) acrylate of bisphenol-A.
As the polymerizable compound of the ethylenic unsaturated bond with more than 3, trimethylolpropane tris (first can be included Base) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, (the first of dipentaerythritol five Base) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol Seven (methyl) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) it is isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified Dipentaerythritol six (methyl) acrylate, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified two season Penta tetrol six (methyl) acrylate, (methyl) acrylate of caprolactone modification pentaerythrite four and the season penta 4 of caprolactone modification two Alcohol six (methyl) acrylate.
In these, (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) third can be preferably included Olefin(e) acid ester.
The weight average molecular weight of polymerizable compound (C) be preferably more than 150 and less than 2900, more preferably more than 250 and Less than 1500.
Relative to the total amount of solid constituent, the polymerizable compound (C) in colored curable resin composition of the invention Containing ratio be usually 1~60 mass %, preferably 5~50 mass %, more preferably 10~40 mass %, more preferably 12~35 mass %.Content ratio (the resin glue (B) of resin glue (B) and polymerizable compound (C)：Polymerism chemical combination Thing (C)) in terms of quality criteria, usually 20：80~80：20, preferably 35：65~80：20.If polymerizable compound (C) Content in above-mentioned scope, then what the chemical-resistant of residual film ratio and colour filter when being formed with colored pattern was improved inclines To.
＜ polymerization initiators (D) ＞
Polymerization initiator (D) triggers polymerization as long as living radical, acid etc. can be produced using light, the effect of heat Compound, then be not particularly limited, known polymerization initiator can be used.
As polymerization initiator (D), preferably comprising selected from alkyl phenyl assimilation compound, triaizine compounds, acyl group oxidation The polymerization initiator of at least one of phosphine compound, O- acyl groups oxime compound and united imidazole, more preferably comprising O- The polymerization initiator of acyl group oxime compound.
As O- acyl group oxime compounds, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) butane -1- can be included Ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methylbenzenes Formoxyl) -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- { 2- methyl -4- (3,3- diformazans Base -2,4- dioxolyls methoxyl group) benzoyl -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl group -1- [9- Ethyl -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines and N- benzoyloxy -1- [9- Ethyl -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines.Irgacure can be used The commercially available products such as (registration mark) OXE01, OXE02 (being manufactured above for BASF AG), N-1919 (manufacture of ADEKA companies).Wherein, It is preferably selected from N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) butane -1- ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines and N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) -3- rings penta It is at least one kind of in base propane -1- ketone -2- imines, more preferably N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- Ketone -2- imines.
As alkyl phenyl assimilation compound, 2- methyl -2- morpholinoes -1- (4- methylsulfanyls phenyl) third can be included Alkane -1- ketone, 2- dimethylaminos -1- (4- morphlinophenyls) -2- benzyls butane -1- ketone and 2- (dimethylamino) -2- [(4- Aminomethyl phenyl) methyl] -1- [4- (4- morpholinyls) phenyl] butane -1- ketone.Usable Irgacure369,907,379 (are above BASF AG manufacture) etc. commercially available product.
Alkyl phenyl assimilation compound can be 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] propane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyls -1- (4- isopropyl alkene Base phenyl) propane -1- ketone oligomer, α, α-diethoxy acetophenone and benzil dimethyl ketal.
As triaizine compounds, can include double (trichloromethyl) -6- (4- the methoxyphenyls) -1,3,5-triazines of 2,4-, Double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of 2,4-, double (the trichloromethyl) -6- piperonyls -1,3,5- of 2,4- Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of triazine, 2,4-, double (trichloromethyl) -6- [2- of 2,4- (5- methylfuran -2- bases) vinyl] -1,3,5- triazines, double (the trichloromethyl) -6- [2- (furans -2- bases) vinyl] of 2,4- - Double (trichloromethyl) -6- [2- (4- diethylamino -2- aminomethyl phenyls) the vinyl] -1,3,5- triazines of 1,3,5- triazines, 2,4- With double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyls) the vinyl] -1,3,5- triazines of 2,4-.
As acylphosphine oxide compound, TMDPO can be included.It can be used The commercially available products such as Irgacure (registration mark) 819 (BASF AG's manufacture).
As united imidazole, specifically, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl connection can be included Imidazoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 Number publication, Japanese Unexamined Patent Publication 6-75373 publications etc.), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines (for example, With reference to Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc.) and 4,4 ', the phenyl of 5,5 '-position The imidazolium compounds replaced by alkoxy carbonyl group (for example, referring to Japanese Unexamined Patent Publication 07-010913 publications etc.).Wherein, preferably by Compound and their mixture that following formula is represented.
As other polymerization initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin can be included The benzoin compound such as isopropyl ether, benzoin isobutyl ether；Benzophenone, o- benzoyl methyl benzoate, 4- phenyl two Benzophenone, -4 '-dimethyl diphenyl sulfide of 4- benzoyls, 3,3 ', 4,4 '-four (tert-butyl crosses oxygen carbonyl) benzophenone and 2, The benzophenone cpds such as 4,6- tri-methyl benzophenones；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- EAQs and camphorquinone；10- Butyl -2- chloro-acridines ketone, benzil, phenylglyoxalates methyl esters and titanocenes compound etc..These preferably with it is described later polymerize draw Hair auxiliary agent (particularly amine system polymerization triggers auxiliary agent) is applied in combination.
The content of polymerization initiator (D), relative to the matter of total amount 100 of resin glue (B) and polymerizable compound (C) Part is measured, usually 0.1~40 mass parts, preferably 0.1~30 mass parts, more preferably 1~30 mass parts, more preferably 1~20 mass parts.
＜ polymerizations trigger auxiliary agent ＞
Polymerization trigger auxiliary agent be in order to promote with polymerization initiator (D) triggered polymerization polymerizable compound (C) gather The compound or sensitizer closed and used.The colored curable resin composition of the present invention triggers the situation of auxiliary agent comprising polymerization Under, generally it is applied in combination with polymerization initiator (D).Trigger auxiliary agent as polymerization, amine system polymerization can be included and trigger auxiliary agent, alcoxyl The polymerization of base anthracene system triggers auxiliary agent, the polymerization of thioxanthones system to trigger auxiliary agent and carboxylic serials polymerization to trigger auxiliary agent.
Trigger auxiliary agent as amine system polymerization, the alkanes such as triethanolamine, methyl diethanolamine and triisopropanolamine can be included Hydramine；4- dimethylaminobenzoic acids methyl esters, EDMAB, 4- dimethylaminobenzoic acids isopentyl ester, The Aminobenzoate such as benzoic acid 2- dimethylamino ethyl esters and 4- dimethylaminobenzoic acid 2- ethylhexyls；N, N- dimethyl Para-totuidine, 4,4 '-bis- (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-bis- (diethylamino) benzophenone With 4,4 '-bis- (ethylmethylamino) benzophenone, wherein it is preferred that 4, the alkyl amino such as 4 '-bis- (diethylamino) benzophenone Benzophenone.Wherein, preferred alkyl amino benzophenone, preferably 4,4 '-bis- (diethylamino) benzophenone.EAB- can be used The commercially available products such as F (hodogaya chemical industry (strain) manufacture).
Trigger auxiliary agent as the polymerization of alkoxy anthracene system, 9,10- dimethoxys anthracene, 2- ethyl -9,10- dimethoxies can be included Base anthracene, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene and the fourths of 2- ethyls -9,10- two Epoxide anthracene.
Trigger auxiliary agent as the polymerization of thioxanthones system, ITX, ITX, 2,4- bis- can be included Ethyl thioxanthones, the clopenthixal ketones of 2,4- bis- and the chloro- 4- propoxythioxanthones of 1-.
Trigger auxiliary agent as carboxylic serials polymerization, Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethyl can be included Phenylsulfanyl acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl vinegar Acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, benzene Epoxide acetic acid, naphthalene sulfenyl acetic acid, N- naphthyls glycine and naphthoxy acetic acid.
Use in the case that polymerization triggers auxiliary agent, its content is relative to resin glue (B) and polymerizable compound (C) The mass parts of total amount 100, preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If polymerization triggers containing for auxiliary agent Amount within the range, can be tended to improve with more high sensitivity formation colored pattern, the productivity ratio of colour filter.
＜ solvents (E) ＞
To solvent (E) and it is not limited, solvent usually used in the field can be used alone or two or more is combined Use.Specifically, ester solvent (including-COO-, the solvent without-O- in intramolecular), ether solvents can be included (in intramolecular bag Solvent containing-O-, without-COO-), ether-ether solvent (in solvent of the intramolecular comprising-COO- and-O-), ketone solvent is (in intramolecular Solvent comprising-CO-, without-COO-), alcoholic solvent (intramolecular include OH, the solvent without-O- ,-CO- and-COO-), virtue Fragrant race's hydrocarbon solvent, amide solvent and dimethyl sulfoxide (DMSO).
As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, acetic acid second can be included Ester, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyric acid Butyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate And gamma-butyrolacton.
As ether solvents, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two can be included Alcohol single-butyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, propylene glycol monomethyl ether, propane diols Single ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, DPGME, DPG n-propyl ether, dipropyl Glycol butyl ether, dipropylene glycol methyl propyl ether, tripropylene glycol monomethyl ether, tripropylene glycol propyl ether, 3- methoxyl group -1- fourths Alcohol, 3- methoxyl group -3- methyl butanols, tetrahydrofuran, oxinane, 1,4- dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl Base ether, diethylene glycol (DEG) methyl ethyl ether, diethylene glycol (DEG) dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl fennel Ether.
As ether-ether solvent, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, second can be included Epoxide methyl acetate, ethyoxyl ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxy-propionic acid first Ester, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxies Base methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, 3- methoxybutyls acetic acid esters, 3- methyl -3- methoxybutyls acetic acid esters, propylene glycol monomethyl ether, propane diols list second Base ether acetic acid ester, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, two Glycol list monoethyl ether acetate, diethylene glycol monobutyl ehter acetic acid esters and dipropylene glycol methyl ether acetic acid esters and propane diols oxalic acid Ester.
As ketone solvent, 4- hydroxy-4-methyl-2-pentanones, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- can be included Heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone and isophorone.
As alcoholic solvent, methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols and sweet can be included Oil.
As aromatic hydrocarbon solvents, benzene,toluene,xylene and 1,3,5- trimethylbenzenes can be included.
As amide solvent, DMF, DMA, N- crassitudes can be included Ketone.
, can be by two kinds of combination of the above for these solvents.
In above-mentioned solvent, from the boiling point under coating, drying property aspect, preferably 1atm (atmospheric pressure) be 120 More than DEG C, less than 210 DEG C of organic solvent.Wherein, preferably propylene glycol monomethyl ether, ethyl lactate, propane diols list first Base ether, 3- ethoxyl ethyl propionates, ethylene glycol single methyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diglycol monotertiary second Base ether, acetic acid 3- methoxybutyls, 3- methoxyl groups-n-butyl alcohol, 4- hydroxy-4-methyl-2-pentanones, propylene-glycol diacetate, N, Dinethylformamide and 1-METHYLPYRROLIDONE, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, second two Alcohol single-butyl ether, dipropylene glycol methyl ether acetic acid esters, ethyl lactate, acetic acid 3- methoxybutyls, 3- methoxyl groups-n-butyl alcohol, 3- Ethoxyl ethyl propionate, N,N-dimethylformamide, 1-METHYLPYRROLIDONE, 4- hydroxy-4-methyl-2-pentanones and propane diols two Acetic acid esters.
Relative to the total amount of colored curable resin composition, the containing ratio of solvent (E) is usually 60~95 mass %, excellent Elect 65~92 mass %, more preferably 70~90 mass % as.If the content of solvent (E) is in above-mentioned scope, during coating Flatness become good, will not be not enough further, since foring during colour filter colour saturation, therefore become good with display characteristic Good tendency.
＜ levelling agents ＞
As levelling agent, silicone based surfactants, fluorine system surfactant and having with fluorine atom can be included Machine silicon systems surfactant.
As silicone based surfactants, the surfactant that there is siloxanes key in intramolecular can be included.Specifically Ground, can include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (Dong Li-DOW CORNING (strain) manufactures), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI Learn industrial (strain) manufacture), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 With TSF4460 (stepping the Japanese contract commercial firm manufacture of figure new high-tech material).
As fluorine system surfactant, the surfactant that there is fluorocarbon chain in intramolecular can be included.Specifically, it can arrange Enumerate Off ロ ラ ー De (registration mark) FC430, FC431 (Sumitomo 3M (strain) manufactures), メ ガ Off ァ ッ Network (registration mark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC (strain) manufactures), エ Off ト ッ プ (registrars Mark) EF301, EF303, EF351, EF352 (Mitsubishi General Materials electronics chemical conversion (strain) manufacture), サ ー Off ロ Application (registration mark) S381, S382, SC101, SC105 (Asahi Glass (strain) manufacture) and E5844 (research of (strain) great Jin fine chemistry industries is manufactured).
As the silicone based surfactants with fluorine atom, can include has siloxanes key and fluorine carbon in intramolecular The surfactant of chain.Specifically, メ ガ Off ァ ッ Network (registration mark) R08, BL20, F475, F477 and F443 can be included (DIC (strain) manufactures).
Relative to the total amount of colored curable resin composition, the containing ratio of levelling agent is usually more than 0.0005 mass % And 0.6 below mass %, preferably more than 0.001 mass % and below 0.5 mass %, more preferably more than 0.001 mass % And 0.2 below mass %, more preferably more than 0.002 mass % and below 0.1 mass %, particularly preferably 0.005 matter Measure more than % and below 0.07 mass %.If the containing ratio of levelling agent is in above-mentioned scope, the flat of colour filter can be made Smooth property becomes good.
Epoxide (P)
As epoxide (P), as long as the compound of the epoxy ethyl with more than 1.But, epoxidation Compound (P) is compounds for example different from resin glue (B).If using such epoxide (P), it is possible to increase The lightness of colored curable resin composition, additionally is able to improve solvent resistance.Further, the epoxy that epoxide (P) has It can be more than 2, or more than 3 as long as the number of ethyl is more than 1.
The acid number of above-mentioned epoxide (P) is preferably, less than 30mg-KOH/g, more preferably below 20mg-KOH/g, to enter One step is preferably below 10mg-KOH/g, particularly preferably 0mg-KOH/g.
As above-mentioned epoxide (P), the epoxides of the (co) polymer of isoprene, butadiene can be included Epoxides of the alkane diene (co) polymer such as epoxides of (co) polymer etc. does not have the epoxide of ring；Have The epoxide of ring.As the ring, ester ring type hydrocarbon ring, aromatic series hydrocarbon ring can be included.These can be heterocycle, but be preferably Hydrocarbon ring.
As ester ring type hydrocarbon ring, can include cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, The cycloalkanes hydrocarbon ring of the carbon numbers such as cyclooctane ring 3~10；The carbon numbers 5~10 such as cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclo-octene ring Cyclenes hydrocarbon ring；Bicyclic [2.2.1] heptane ring (norbornane ring), bicyclic [2.2.1] heptane ring (isoborneol of 1,7,7- trimethyls Alkane ring), bicyclic [2.2.2] octane ring, three ring [5.2.1.02,6] decane ring, three ring [3.3.1.13,7] decane ring (adamantane ring) Polycyclic ester ring type hydrocarbon ring Deng carbon number 7~15 etc..
Ester ring type hydrocarbon ring is preferably the cycloalkanes hydrocarbon ring of the cycloalkanes hydrocarbon ring of carbon number 4~9, more preferably carbon number 5~8.Wherein, more It is preferred that hexamethylene.
As aromatic series hydrocarbon ring, phenyl ring, naphthalene nucleus and anthracene nucleus etc. can be included.
As the epoxide with ring, the chemical combination preferably with the ring of more than 1 and the epoxy ethyl of more than 2 Thing, the epoxide more preferably with the ring of more than 2 and the epoxy ethyl of more than 2.In the epoxide with ring In, the number relative to the epoxy ethyl of the number 1 of ring is preferably 0.8~1.2, and more preferably 0.9~1.1.
As the epoxide with ester ring type hydrocarbon ring and the epoxy ethyl of more than 2, the double (hydroxyls of 2,2- can be included Methyl)-n-butyl alcohol 1,2- epoxies -4- (2- epoxy ethyls) hexamethylene addition product etc..
As above-mentioned epoxide, 3,4- 7-oxa-bicyclo[4.1.0 carboxylic acid 3', 4'- epoxycyclohexanecarboxylates can be also included (セ ロ キ サ イ De 2021P, the manufacture of Daicel Co., Ltd.), 6-caprolactone are modified 3,4- 7-oxa-bicyclo[4.1.0 carboxylic acid 3', 4'- rings Oxygen cyclohexylmethyl (セ ロ キ サ イ De 2081, the manufacture of Daicel Co., Ltd.) etc..
As the epoxide with aromatic series hydrocarbon ring and the epoxy ethyl of more than 2, bisphenol type epoxy can be included The bisphenol types such as compound, bisphenol F type epoxy compound, bmminated bisphenol-A type epoxide and brominated bisphenol F type epoxides Epoxide；The nobolak type epoxy such as phenol novolak-type epoxy compound and cresol novolak type epoxy compound Compound；Biphenyl type epoxy compound；Trihydroxy benzene methylmethane type epoxide；Four phenol ethane type epoxides；Benzene second The styrenic such as the epoxides of alkene-butadiene copolymer and the epoxides of styrene-isoprene copolymer Epoxides etc..Wherein, particularly preferred bisphenol A type epoxy compound and ortho cresol novolak type epoxide.
The weight average molecular weight of epoxide (P) is preferably less than 7000, and more preferably less than 5000, more preferably Less than 2900, preferably more than 50, more preferably more than 200, more preferably more than 350.
The epoxide equivalent of epoxide (P) is preferably more preferably 50g/ more than 30g/ equivalents and below 400g/ equivalents More than equivalent and below 350g/ equivalents, more preferably more than 100g/ equivalents and below 300g/ equivalents, particularly preferably More than 150g/ equivalents and below 250g/ equivalents.Epoxide equivalent can use method specified in JISK7236 to determine.
The containing ratio of epoxide (P), it is excellent in the mass % of colored curable resin composition (solid constituent) 100 Elect as more than 0.1 mass % and below 25 mass %, more preferably more than 0.5 mass % and below 20 mass %, it is further excellent Elect as more than 1 mass % and below 15 mass %, particularly preferably more than 2 mass % and below 10 mass %.
＜ other compositions ＞
The colored curable resin composition of the present invention, as needed, can include filler, other macromolecule chemical combination In the technical fields such as thing, closely sealed accelerator, antioxidant, light stabilizer, chain-transferring agent, epoxy hardener, curing accelerator Known additive.
The manufacture method ＞ of ＜ colored curable resin compositions
The colored curable resin composition of the present invention for example can be by by colouring agent (A), resin glue (B), poly- Conjunction property compound (C), polymerization initiator (D), epoxide (P) and solvent (E) as needed, levelling agent, polymerization are drawn Hair auxiliary agent and other compositions are mixed and prepared.For mixed colored curable resin composition, preferably with aperture 0.01~ 10 μm or so of filter filtering.
The manufacture method ＞ of ＜ colour filters
Colored pattern can be formed by the colored curable resin composition of the present invention, as its manufacture method, can be enumerated Go out photoetching process, ink-jet method, print process etc., preferably include photoetching process.Photoetching process is to be coated with colored curable resin composition In substrate, dry and form coloring compositions nitride layer, the method that the coloring compositions nitride layer is exposed via photomask, developed.Photoetching In method, by without using photomask and/or not developing in exposure, so as to form consolidating as above-mentioned coloring compositions nitride layer The coloring film of compound.Colored pattern, the coloring film so formed is colour filter of the invention.
The thickness of the colour filter of making, can suitably adjust according to purpose, purposes etc., usually 0.1~30 μm, be preferably 0.1~20 μm, more preferably 0.5~6 μm.
As substrate, glass plate, resin plate can be used, silicon, aluminium, silver, silver/copper/palldium alloy are formd on aforesaid substrate The product of film etc..Other color-filter layer, resin bed, transistor, circuit etc. can be formed on these substrates.
Using photolithographic each color pixel formed can known or usual device, under the conditions of carry out.For example, can It is as described below to make.
First, colored curable resin composition is coated on substrate, passes through heat drying (prebake) and/or decompression Dry, so that the volatile ingredients such as solvent be removed and dried, obtain smooth coloring compositions nitride layer.As coating method, it can arrange Enumerate spin-coating method, slot coated method and slit and method of spin coating.
Next, being exposed via the photomask of the colored pattern for forming target to coloured composition layer.Due to Parallel rays can equably be irradiated to plane of exposure entirety, photomask can be carried out and the substrate of coloring compositions nitride layer is formd Correctly align, therefore preferably use the exposure devices such as mask aligner and stepper and be exposed.By making the coloring after exposure Composition layer is contacted and developed with developer solution, so as to form colored pattern on substrate.By development, coloring compositions nitride layer is not Exposure portion dissolves and is removed in developer solution.
As developer solution, the preferred alkali compounds such as potassium hydroxide, sodium acid carbonate, sodium carbonate, tetramethyl ammonium hydroxide The aqueous solution.
Developing method can be any of sheathed immersion method, infusion process and spray-on process.And then, it can make substrate in development Tilt arbitrary angle.Preferably washed after development.
The colored pattern that preferred pair is obtained is bakeed after further carrying out.For with the colored pattern, coloring so obtained The colour filter of film, in order to assign various characteristics, can further carry out surface coating processing.
The colour filter formed by the colored curable resin composition of the present invention can be used as in display device (for example, liquid crystal Display device, organic el device, Electronic Paper etc.) and solid-state imager in the colour filter that uses.
Embodiment
The present invention is illustrated in more detail by the following examples, but the present invention is not limited by these embodiments.Show In example, as long as no special instructions, it is quality criteria to represent content or even the % of usage amount and part.
Synthesis example 1 (pigment synthesis example)
Following reaction is carried out under nitrogen atmosphere.Methylphenylamine is put into possessing the flask of cooling tube and agitating device It is after 15.3 parts of (Tokyo HuaCheng Industry Co., Ltd's manufacture) and 60 parts of DMF, mixed solution is ice-cold.In ice 30 minutes are lasted under cold and is little by little added after 5.7 parts of 60% sodium hydride (Tokyo HuaCheng Industry Co., Ltd's manufacture), side heating Stirred 1 hour to room temperature side.Little by little by 4,4 '-difluoro benzophenone (Tokyo HuaCheng Industry Co., Ltd's manufacture) 10.4 Part is added in reaction solution, has been stirred at room temperature 24 hours.Reaction solution is little by little added after 200 parts of frozen water, at room temperature 15 hours are stood, if water removed by being decanted, sticky solid has been obtained as residue.Added in the sticky solid After 60 parts of methanol, it has been stirred at room temperature 15 hours.It is refined with column chromatography after the solid of precipitation is separated by filtration.By what is refined Faint yellow solid is dried at 60 DEG C under reduced pressure, has obtained 9.8 parts of the compound represented by formula (C-I-18).
Following reaction is carried out under nitrogen atmosphere.Put into possessing the flask of cooling tube and agitating device by formula (B-I- 7) after 20 parts of 8.2 parts of compound representing, 10 parts of the compound represented by formula (C-I-18) and toluene, next, adding oxygen chlorine Change 12.2 parts of phosphorus, stirred at 95~100 DEG C 3 hours.Next, reactant mixture is cooled to after room temperature, isopropanol is used 170 parts of dilutions.Next, after the reaction solution of dilution is injected in 300 parts of saturated aqueous common salt, adding 100 parts of toluene, stirring 30 minutes.Then, stop stirring, stand 30 minutes, be as a result separated into organic layer and water layer.Water layer is discarded by a point liquid operation Afterwards, by organic layer 300 parts of cleanings of saturated aqueous common salt.The saltcake of appropriate amount is added in organic layer, has stirred after 30 minutes, has obtained Filtering, the organic layer dried are arrived.Solvent distillation is carried out to obtained organic layer using evaporator, blue or green violet solid has been obtained. And then, blue or green violet solid is dried at 60 DEG C under reduced pressure, the compound 18.4 represented by formula (A-II-18) has been obtained Part.
Following reaction is carried out under nitrogen atmosphere.Put into possessing the flask of cooling tube and agitating device by formula (A-II- 18) after 8 parts of the compound of expression, 396 parts of methanol, it is stirred at room temperature 30 minutes, is prepared for cyan solution.Next, in green grass or young crops Put into after 396 parts of water, and then be stirred at room temperature 30 minutes in color solution, obtained reaction solution.Water 53 is put into beaker Part, and then 53 parts of 11.8 parts of Keggin-type phosphotungstic acid (Aldrich manufacture) and methanol are put into the water, in air atmosphere Under, mix at room temperature, be prepared for Salkowski's solution.
1 hour is lasted to instill obtained Salkowski's solution in reaction solution prepared above.And then be stirred at room temperature After 30 minutes, filtering has obtained cyan solid.Obtained cyan solid is put into 200 parts of methanol, makes it scattered 1 hour Afterwards, filtered, by the operation 2 times repeatedly.The cyan solid obtained by the operation is put into 200, water, makes its point After dissipating 1 hour, filtered, by the operation 2 times repeatedly.By the cyan solid obtained by the operation under reduced pressure at 60 DEG C Lower drying, has obtained 17.1 parts of the compound represented by formula (A-I-18).
Synthesis example 2 (resin used in color dispersion liquid)
In the flask for possessing reflux condenser, dropping funel and agitator, make nitrogen so that 0.02L/ is diverted into and turns into nitrogen Atmosphere, is put into 105 parts of 3- methoxyl groups -200 parts of n-butyl alcohol and acetic acid 3- methoxybutyls, 70 DEG C is heated to while stirring.Connect down Come, by 60 parts of methacrylic acid, acrylic acid 3, the ring [5.2.1.0 of 4- epoxies three2,6] the last of the ten Heavenly stems ester (compound represented by formula (II-1) With the mol ratio 50 of the compound represented by formula (III-1)：50 mixture) 240 parts be dissolved in acetic acid 3- methoxybutyls 140 Part, prepare solution, using dropping funel, last 4 hours by the lysate instill be incubated in 70 DEG C of flask.On the other hand, Using other dropping funel last 4 hours by polymerization initiator 2,2 '-azo two (2,4- methyl pentane nitriles) 30 parts be dissolved in The solution of 225 parts of acetic acid 3- methoxybutyls is instilled in flask.After the instillation of the solution of polymerization initiator terminates, in 70 DEG C of holdings 4 hours, room temperature is then cooled to, solid constituent 32.6%, acid number 110mg-KOH/g (solid constituent conversion) resin has been obtained B-1b solution.Obtained resin B -1b weight average molecular weight Mw is 13400, and molecular weight distribution is 2.50.
The preparation ＞ of ＜ color dispersion liquid
By 10 parts of the compound by formula (A-I-18) expression, dispersant (BYK (registration mark)-LPN6919 (PVC ッ Network ケ ミ ー ジ ャ パ Application company manufactures)) 2 parts, 4 parts of resin B -1b (solid constituent conversion), 84 parts of propylene glycol monomethyl ether With 0.2mm 300 parts of mixing of zirconium oxide bead, using coating conditioner (manufacture of Red Devil companies), after vibrating 6 hours, lead to Filtering removes zirconium oxide bead, so as to be prepared for color dispersion liquid (1).
Synthesis example 3 has been obtained by formula using the method described in the synthesis example 3 of Japanese Unexamined Patent Publication 2013-122577 publications The compound that (1-32) is represented.
Synthesis example 4
In the flask for possessing reflux condenser, dropping funel and agitator, appropriate nitrogen is set to flow into and be replaced into blanket of nitrogen, 141 parts of ethyl lactate, 178 parts of propylene glycol monomethyl ether are put into, 85 DEG C are heated to while stirring.Next, it is small to last 5 When by 38 parts of acrylic acid, the ring [5.2.1.0 of acrylic acid 3,4- epoxies three2,6] decyl- 8 and 9- base esters 25 parts of mixture, cyclohexyl horse Come 137 parts of acid imide, 50 parts of 2-hydroxyethyl methacrylate, the mixed solution drop of 338 parts of propylene glycol monomethyl ether Enter.On the other hand, last instillation in 6 hours and 2,2- azodiisobutyronitriles are dissolved in 88 parts of propylene glycol monomethyl ether for 5 parts In mixed solution.After instillation terminates, maintain at the same temperature after 4 hours, be cooled to room temperature, obtained Type B viscosity (23 DEG C) 22mPas, solid constituent 25.5%, solid constituent acid number 111mg-KOH/g copolymer (B-1) solution.The copolymerization of generation The weight average molecular weight Mw of thing is 7700, and decentralization is 2.1.
The measure of weight average molecular weight (Mw) and number-average molecular weight (Mn) for above-mentioned resin glue, using GPC method, Carry out under the following conditions.
Device；K2479 (manufacture of (strain) Shimadzu Seisakusho Ltd.)
Post；SHIMADZU Shim-pack GPC-80M
Column temperature；40℃
Solvent；THF (tetrahydrofuran)
It is detected liquid concentration：25mg/mL (solvents；THF)
Flow velocity：1.0mL/min
Detector：RI
Correction standard substance：TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500 (eastern Cao's (strain) manufacture)
The ratio between weight average molecular weight and number-average molecular weight that polystyrene obtained above is converted are used as decentralization (Mw/ Mn)。
Embodiment 1
(preparation of colored curable resin composition 1)
Mixing, has obtained colored curable resin composition 1.
Embodiment 2
(preparation of colored curable resin composition 2)
Mixing, has obtained colored curable resin composition 2.
Embodiment 3
(preparation of colored curable resin composition 3)
Mixing, has obtained colored curable resin composition 3.
Comparative example 1
By (A) colouring agent；C.I. pigment blue 15：6 29.3 parts of (pigment)
10 parts of acrylic acid series pigment dispersing agent
194 parts of propylene glycol monomethyl ether
Mixing, disperses pigment using ball mill, then,
Mixing, has obtained colored curable resin composition 4.
The making ＞ of ＜ colour filters (colored pattern)
In the glass substrate (Eagle 2000 of 5cm square；Corning Incorporated manufacture) on using spin-coating method be coated with staining and curing After property resin combination 1, the prebake 3 minutes at 100 DEG C forms coloring compositions nitride layer.After letting cool, make to form the coloring The substrate of composition layer, at intervals of 80 μm, uses exposure machine (TME-150RSK with quartz glass photomask；トプコン (strain) is manufactured), under air atmosphere, with 35mJ/cm2Light exposure (365nm benchmark) carry out light irradiation.As photomask, make With the photomask for foring 50 μm of lines and space pattern.By the coloring compositions nitride layer after light irradiation in developer solution (with quality point Rate meter, the respectively aqueous solution comprising potassium hydroxide 0.05% and sodium butylnaphthalenesulfonate 0.2%) at 25 DEG C immersion development 60 Second, after washing, bakee in an oven, after being carried out 30 minutes at 230 DEG C, obtained colored pattern.
For colored curable resin composition 2~4, colored pattern has similarly been obtained.
＜ film thickness measuring ＞
For obtained each colored pattern, film thickness measuring device (DEKTAK3 is used；Japanese vacuum technique (strain) manufacture)) Determine thickness.Show the result in table 5.
＜ chromaticity evaluations ＞
For obtained each colored pattern, colour examining machine (OSP-SP-200 is used；Olympus (strain) is manufactured) light splitting is determined, Using the characterisitic function of illuminant-C, the Y in xy chromaticity coordinates (x, y) and the tristimulus values in CIE XYZ color specification systems is determined.Y It is bigger, represent that lightness is higher.Show the result in table 5.
The preparation ＞ of ＜ colour filters (coloring film)
In the glass substrate (Eagle 2000 of 5cm square；Corning Incorporated manufacture) on using spin-coating method be coated with staining and curing After property resin combination 1, the prebake 3 minutes at 100 DEG C forms coloring compositions nitride layer.After letting cool, make to form the coloring The substrate of composition layer, at intervals of 80 μm, uses exposure machine (TME-150RSK with quartz glass photomask；トプコン (strain) is manufactured), under air atmosphere, with 35mJ/cm2Light exposure (365nm benchmark) to coloured composition layer carry out light irradiation. As photomask, the photomask for foring 50 μm of lines and space pattern has been used.By in an oven, 30 points are carried out at 230 DEG C Bakeed after clock, so as to obtain coloring film.
Coloring film has similarly been obtained for colored curable resin composition 2~4.
＜ solvent resistances evaluate ＞
Use colour examining machine (OSP-SP-200；OLYMPUS companies manufacture) determine the obtained colourity for colouring film.Connect , obtained coloring film kept at 23 DEG C to impregnate 30 minutes in constant significantly excessive METHYLPYRROLIDONE, Similarly determine the colourity of the coloring film after dipping.
As the evaluation criterion of aberration, if Δ Eab* is less than 3, tone variations are not almost found, work is shown Good characteristic during for colour filter, if Δ Eab* is able to confirm that tone variations more than 3, this has when being as colour filter The level of problem.Show the result in table 5.
【Table 5】
Industrial applicability
Using the colored curable resin composition of the present invention, it can be formed with high brightness and solvent resistance is good Colour filter.

Claims (5)

1. colored curable resin composition, it is to contain colouring agent (A), resin glue (B), polymerizable compound (C), poly- The colored curable resin composition of initiator (D) and epoxide (P) is closed, wherein, epoxide (P) and binding agent tree Fat (B) is different, and colouring agent (A) is the colouring agent of inclusion compound (Aa), compound (Aa) by the cation with pigment skeleton, With from containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and the anion of the compound of oxygen composition, relative to The total amount of toner (A), the containing ratio of epoxide (P) is more than 0.1 mass % and below 60 mass %.
2. colored curable resin composition according to claim 1, wherein, resin glue (B) be with come since The construction unit (a) of at least one kind of monomer selected in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and from olefinic insatiable hunger With key and the copolymer of the construction unit (b) of the monomer of ring-type ether structure.
3. colored curable resin composition according to claim 1, wherein, by the cation with pigment skeleton and From the compound (Aa) containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and the anion of the compound of oxygen composition For the compound represented by formula (A-I)：
In formula (A-I), R41~R44Independently of each other represent the amino that can be substituted or can be substituted with halogen atoms carbon number 1~ The base that contained methylene is replaced by oxygen atom in 20 saturated hydrocarbyl, the alkyl of carbon number 2~20, the alkyl of the carbon number 2~20 Group, the aromatic hydrocarbyl can with substituent, the aralkyl or hydrogen atom can with substituent, R41With R42Can combine and and it The nitrogen-atoms that combines form ring, R together43With R44It can combine and form ring together with the nitrogen-atoms that they are combined,
R47~R54The alkyl of hydrogen atom, halogen atom, nitro, hydroxyl or carbon number 1~8 is represented independently of each other, is constituting the alkane Oxygen atom, R are can be inserted between the methylene of base48With R52It can be combined with each other and form-NH- ,-O- ,-S- or-SO2-,
R41~R44And R47~R54In, adjacent methylene will not be replaced by oxygen atom simultaneously, in addition, the Asia of the end of alkyl Methyl will not also be replaced by oxygen atom,
Ring T1Represent there can be the heteroaromatic of substituent,
[Y]m-Represent containing at least one element and the anion of the m valencys of oxygen in tungsten, molybdenum, silicon and phosphorus,
M represents 2~14 integer,
Further, in the case of containing multiple cations represented by following formula in 1 molecule, they can be identical knot Structure, or different structures,
In formula, ring T1、R41~R44And R47~R54Respectively with it is above-mentioned synonymous.
4. the colour filter formed as the colored curable resin composition according to any one of claims 1 to 3.
5. liquid crystal display device, it includes colour filter according to claim 4.
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